National Library of Energy BETA

Sample records for metal organic frameworks

  1. Gas adsorption on metal-organic frameworks

    DOE Patents [OSTI]

    Willis, Richard R.; Low, John J. , Faheem, Syed A.; Benin, Annabelle I.; Snurr, Randall Q.; Yazaydin, Ahmet Ozgur

    2012-07-24

    The present invention involves the use of certain metal organic frameworks that have been treated with water or another metal titrant in the storage of carbon dioxide. The capacity of these frameworks is significantly increased through this treatment.

  2. Isomerism in Metal-Organic Frameworks: "Framework Isomers" |...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Isomerism in Metal-Organic Frameworks: "Framework Isomers" Previous Next List Trevor A. Makal, Andrey A. Yakovenko, and Hong-Cai Zhou, J. Phys. Chem. Lett., 2011, 2 (14), pp ...

  3. A Route to Metal-Organic Frameworks through Framework Templating...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    A Route to Metal-Organic Frameworks through Framework Templating Previous Next List Zhangwen Wei, Weigang Lu, Hai-Long Jiang, and Hong-Cai Zhou, Inorg. Chem., 2013, 52 (3), pp ...

  4. Metal-organic frameworks with exceptionally large pore aperatures

    DOE Patents [OSTI]

    Yaghi, Omar M.; Furukawa, Hiroyasu; Deng, Hexiang

    2015-07-14

    The disclosure relates to metal organic frameworks or isoreticular metal organic frameworks, methods of production thereof, and methods of use thereof.

  5. Tunable Electrical Conductivity in Metal-Organic Framework Thin...

    Office of Scientific and Technical Information (OSTI)

    Tunable Electrical Conductivity in Metal-Organic Framework Thin-Film Devices Citation Details In-Document Search Title: Tunable Electrical Conductivity in Metal-Organic Framework...

  6. Metal Insertion in a Microporous Metal-Organic Framework Lined...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Metal Insertion in a Microporous Metal-Organic Framework Lined with 2,2 '-Bipyridine Previous Next List E. D. Bloch, D. Britt, C. Lee, C. J. Doonan, F. J. Uribe-Romo, H. Furukawa, ...

  7. Interpenetration control in metal-organic frameworks for functional...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Interpenetration control in metal-organic frameworks for functional applications Previous ... gas uptake capabilities and catalysis) caused by framework interpenetration. ...

  8. Ultrastable Polymolybdate-Based Metal-Organic Frameworks as Highly...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Ultrastable Polymolybdate-Based Metal-Organic Frameworks as Highly Active Electrocatalysts for Hydrogen Generation...

  9. Tuning the Topology and Functionality of Metal-Organic Frameworks...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Tuning the Topology and Functionality of Metal-Organic Frameworks by Ligand Design Previous ... size and effectively introduce unsaturated metal centers (UMCs) into the framework. ...

  10. Noble Gas Adsorption in Metal-Organic Frameworks Containing Open...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Noble Gas Adsorption in Metal-Organic Frameworks Containing Open Metal Sites Previous Next ... accessibility in this topology enhance the framework interaction with the noble gases. ...

  11. In silico screening of metal-organic frameworks in separation...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    frameworks in separation applications Abstract: Porous materials such as metal-organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs) offer considerable...

  12. Anion separation with metal-organic frameworks

    SciTech Connect (OSTI)

    Custelcean, Radu; Moyer, Bruce A

    2007-01-01

    The application of metal-organic frameworks (MOFs) to anion separations with a special emphasis on anion selectivity is reviewed. The coordination frameworks are classified on the basis of the main interactions to the included anion, from weak and non-specific van der Waals forces to more specific interactions such as coordination to Lewis acid metal centers or hydrogen bonding. The importance of anion solvation phenomena to the observed anion selectivities is highlighted, and strategies for reversing the Hofmeister bias that favors large, less hydrophilic anions, and for obtaining peak selectivities based on shape recognition are delineated. Functionalization of the anion-binding sites in MOFs with strong and directional hydrogen-bonding groups that are complementary to the included anion, combined with organizational rigidity of the coordination framework, appears to be the most promising approach for achieving non-Hofmeister selectivity.

  13. Purification of metal-organic framework materials

    SciTech Connect (OSTI)

    Farha, Omar K.; Hupp, Joseph T.

    2015-06-30

    A method of purification of a solid mixture of a metal-organic framework (MOF) material and an unwanted second material by disposing the solid mixture in a liquid separation medium having a density that lies between those of the wanted MOF material and the unwanted material, whereby the solid mixture separates by density differences into a fraction of wanted MOF material and another fraction of unwanted material.

  14. Purification of metal-organic framework materials

    SciTech Connect (OSTI)

    Farha, Omar K.; Hupp, Joseph T.

    2012-12-04

    A method of purification of a solid mixture of a metal-organic framework (MOF) material and an unwanted second material by disposing the solid mixture in a liquid separation medium having a density that lies between those of the wanted MOF material and the unwanted material, whereby the solid mixture separates by density differences into a fraction of wanted MOF material and another fraction of unwanted material.

  15. Highly Potent Bactericidal Activity of Porous Metal-Organic Frameworks...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Highly Potent Bactericidal Activity of Porous Metal-Organic Frameworks Previous Next List ... A novel cobalt (Co) based metal-organic framework (MOF) was tested and shown to be ...

  16. Brnsted Acidity in Metal-Organic Frameworks | Center for Gas...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Brnsted Acidity in Metal-Organic Frameworks Previous Next List Jiang, Juncong and Yaghi, Omar, M. Bronsted Acidity in Metal-Organic Frameworks. Chem. Rev., 115, 6966-6997 (2015)....

  17. Metal-Organic Frameworks with Precisely Designed Interior for...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Metal-Organic Frameworks with Precisely Designed Interior for Carbon Dioxide Capture in the Presence of Water...

  18. Luminescent metal-organic frameworks (MOFs); a nanolaboratory...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Luminescent metal-organic frameworks (MOFs); a nanolaboratory for photophysics February 7, ... among the components of the framework at several length scales and structural ...

  19. Understanding Small-Molecule Interactions in Metal-Organic Frameworks...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Understanding Small-Molecule Interactions in Metal-Organic Frameworks: Coupling Experiment ... guest molecules and the internal surface of the framework must first be understood. ...

  20. Increasing the Stability of Metal-Organic Frameworks | Center...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Increasing the Stability of Metal-Organic Frameworks Previous Next List Mathieu Bosch, Muwei ... However, the robustness and reactivity of a given framework are largely dependent on ...

  1. Tuning the Formations of Metal-Organic Frameworks by Modification...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Tuning the Formations of Metal-Organic Frameworks by Modification of Ratio of Reactant, ... (3D) framework structure with one-dimensional (1D) honeycomb channels. ...

  2. Stepwise Synthesis of Robust Metal-Organic Frameworks via Postsyntheti...

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    Stepwise Synthesis of Robust Metal-Organic Frameworks via Postsynthetic Metathesis and Oxidation of Metal Nodes in a Single-Crystal to Single-Crystal Transformation Previous Next...

  3. Thermodynamics of metal-organic frameworks

    SciTech Connect (OSTI)

    Wu, Di; Navrotsky, Alexandra

    2015-03-15

    Although there have been extensive studies over the past decade in the synthesis and application of metal-organic frameworks (MOFs), investigation of their thermodynamic stability and of the energetics of guest–host interactions has been much more limited. This review summarizes recent progress in experimental (calorimetric) determination of the thermodynamics of MOF materials. The enthalpies of MOFs relative to dense phase assemblages suggest only modest metastability, with a general increase of enthalpy with increasing molar volume, which becomes less pronounced at higher porosity. The energy landscape of nanoporous materials (inorganic and hybrid) consists of a pair of parallel patterns within a fairly narrow range of metastability of 5–30 kJ per mole of tetrahedra in zeolites and mesoporous silicas or per mole of metal in MOFs. Thus strong thermodynamic instability does not seem to limit framework formation. There are strong interactions within the chemisorption range for small molecule–MOF interactions with defined chemical binding at the metal centers or other specific locations. Coexistence of surface binding and confinement can lead to much stronger guest–host interactions. - Graphical abstract: Energy landscape of inorganic and hybrid porous materials. - Highlights: • Thermochemical data on various MOF structures were experimentally determined. • MOFs are moderately unstable relative to their dense phase assemblage. • Overall energetic landscape of porous materials was revealed. • Guest–host interactions in MOFs were evaluated directly using calorimetry. • Confinement effect and defined chemical binding lead to strong interactions.

  4. Metal–Organic Frameworks Stabilize Solution-Inaccessible Cobalt...

    Office of Scientific and Technical Information (OSTI)

    MetalOrganic Frameworks Stabilize Solution-Inaccessible Cobalt Catalysts for Highly Efficient Broad-Scope Organic Transformations Citation Details In-Document Search Title: ...

  5. Mail-Order Metal-Organic Frameworks (MOFs): Designing Isoreticular...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Mail-Order Metal-Organic Frameworks (MOFs): Designing Isoreticular MOF-5 Analogues Comprising Commercially Available Organic Molecules Previous Next List R. L. Martin, L.-C. Lin,...

  6. Tunable electrical conductivity in metal-organic framework thin...

    Office of Scientific and Technical Information (OSTI)

    A composition including a porous metal organic framework (MOF) including an open metal site and a guest species capable of charge transfer that can coordinate with the open metal ...

  7. An Electrically Switchable Metal-Organic Framework

    SciTech Connect (OSTI)

    Fernandez, Carlos A.; Martin, Paul F.; Schaef, Herbert T.; Bowden, Mark E.; Thallapally, Praveen K.; Dang, Liem X.; Xu, Wu; Chen, Xilin; McGrail, B. Peter

    2014-08-19

    Crystalline metal organic framework (MOF) materials containing interconnected porosity can be chemically modified to promote stimulus-driven (light, magnetic or electric fields) structural transformations that can be used in a number of devices. Innovative research strategies are now focused on understanding the role of chemical bond manipulation to reversibly alter the free volume in such structures of critical importance for electro-catalysis, molecular electronics, energy storage technologies, sensor devices and smart membranes. In this letter, we study the mechanism for which an electrically switchable MOF composed of Cu(TCNQ) (TCNQ 5 7,7,8,8-tetracyanoquinodimethane) transitions from a high-resistance state to a conducting state in a reversible fashion by an applied potential. The actual mechanism for this reversible electrical switching is still not understood even though a number of reports are available describing the application of electric-field-induced switching of Cu(TCNQ) in device fabrication.

  8. An Electrically Switchable Metal-Organic Framework

    SciTech Connect (OSTI)

    Fernandez, CA; Martin, PC; Schaef, T; Bowden, ME; Thallapally, PK; Dang, L; Xu, W; Chen, XL; McGrail, BP

    2014-08-19

    Crystalline metal organic framework (MOF) materials containing interconnected porosity can be chemically modified to promote stimulus-driven (light, magnetic or electric fields) structural transformations that can be used in a number of devices. Innovative research strategies are now focused on understanding the role of chemical bond manipulation to reversibly alter the free volume in such structures of critical importance for electro-catalysis, molecular electronics, energy storage technologies, sensor devices and smart membranes. In this letter, we study the mechanism for which an electrically switchable MOF composed of Cu(TCNQ) (TCNQ = 7,7,8,8-tetracyanoquinodimethane) transitions from a high-resistance state to a conducting state in a reversible fashion by an applied potential. The actual mechanism for this reversible electrical switching is still not understood even though a number of reports are available describing the application of electric-field-induced switching of Cu(TCNQ) in device fabrication.

  9. Metal-organic framework materials with ultrahigh surface areas

    SciTech Connect (OSTI)

    Farha, Omar K.; Hupp, Joseph T.; Wilmer, Christopher E.; Eryazici, Ibrahim; Snurr, Randall Q.; Gomez-Gualdron, Diego A.; Borah, Bhaskarjyoti

    2015-12-22

    A metal organic framework (MOF) material including a Brunauer-Emmett-Teller (BET) surface area greater than 7,010 m.sup.2/g. Also a metal organic framework (MOF) material including hexa-carboxylated linkers including alkyne bond. Also a metal organic framework (MOF) material including three types of cuboctahedron cages fused to provide continuous channels. Also a method of making a metal organic framework (MOF) material including saponifying hexaester precursors having alkyne bonds to form a plurality of hexa-carboxylated linkers including alkyne bonds and performing a solvothermal reaction with the plurality of hexa-carboxylated linkers and one or more metal containing compounds to form the MOF material.

  10. Metal Organic Framework Research: High Throughput Discovery of Robust Metal Organic Framework for CO2 Capture

    SciTech Connect (OSTI)

    2010-08-01

    IMPACCT Project: LBNL is developing a method for identifying the best metal organic frameworks for use in capturing CO2 from the flue gas of coal-fired power plants. Metal organic frameworks are porous, crystalline compounds that, based on their chemical structure, vary considerably in terms of their capacity to grab hold of passing CO2 molecules and their ability to withstand the harsh conditions found in the gas exhaust of coal-fired power plants. Owing primarily to their high tunability, metal organic frameworks can have an incredibly wide range of different chemical and physical properties, so identifying the best to use for CO2 capture and storage can be a difficult task. LBNL uses high-throughput instrumentation to analyze nearly 100 materials at a time, screening them for the characteristics that optimize their ability to selectively adsorb CO2 from coal exhaust. Their work will identify the most promising frameworks and accelerate their large-scale commercial development to benefit further research into reducing the cost of CO2 capture and storage.

  11. Hydrogen Storage in Metal-Organic Frameworks

    SciTech Connect (OSTI)

    Omar M. Yaghi

    2012-04-26

    Conventional storage of large amounts of hydrogen in its molecular form is difficult and expensive because it requires employing either extremely high pressure gas or very low temperature liquid. Because of the importance of hydrogen as a fuel, the DOE has set system targets for hydrogen storage of gravimetric (5.5 wt%) and volumetric (40 g L-1) densities to be achieved by 2015. Given that these are system goals, a practical material will need to have higher capacity when the weight of the tank and associated cooling or regeneration system is considered. The size and weight of these components will vary substantially depending on whether the material operates by a chemisorption or physisorption mechanism. In the latter case, metal-organic frameworks (MOFs) have recently been identified as promising adsorbents for hydrogen storage, although little data is available for their sorption behavior. This grant was focused on the study of MOFs with these specific objectives. (1) To examine the effects of functionalization, catenation, and variation of the metal oxide and organic linkers on the low-pressure hydrogen adsorption properties of MOFs. (2) To develop a strategy for producing MOFs with high surface area and porosity to reduce the dead space and increase the hydrogen storage capacity per unit volume. (3) To functionalize MOFs by post synthetic functionalization with metals to improve the adsorption enthalpy of hydrogen for the room temperature hydrogen storage. This effort demonstrated the importance of open metal sites to improve the adsorption enthalpy by the systematic study, and this is also the origin of the new strategy, which termed isoreticular functionalization and metalation. However, a large pore volume is still a prerequisite feature. Based on our principle to design highly porous MOFs, guest-free MOFs with ultrahigh porosity have been experimentally synthesized. MOF-210, whose BET surface area is 6240 m2 g-1 (the highest among porous solids), takes up

  12. Water Adsorption in Metal-Organic Frameworks with Open-Metal...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Water Adsorption in Metal-Organic Frameworks with Open-Metal Sites Previous Next List Xuan ... frameworks (MOFs) by using molecular simulations with different water models. ...

  13. Applying Metal-Organic Frameworks in heterogeneous Catalyisis...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Metal-Organic Frameworks in heterogeneous Catalyisis To control heterogeneous catalysis at atomic and electronic-level represents one of the most challenge research areas....

  14. Photochromic Metal-Organic Frameworks: Reversible Control of...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Photochromic Metal-Organic Frameworks: Reversible Control of Singlet Oxygen Generation Previous Next List Jihye Park, Dawei Feng, Shuai Yuan and Hong-Cai Zhou, Angew. Chem. Int....

  15. Highly porous metal-organic framework sustained with 12-connected...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Highly porous metal-organic framework sustained with 12-connected nanoscopic octahedra Previous Next List Weigang Lu , Daqiang Yuan , Trevor A. Makal , Zhangwen Wei , Jian-Rong Li ...

  16. A Single Crystalline Porphyrinic Titanium Metal-Organic Framework...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Single Crystalline Porphyrinic Titanium Metal-Organic Framework Previous Next List Yuan, Shuai; Liu, Tian-Fu; Feng, Dawei; Tian, Jian; Wang, Kecheng; Qin, Junsheng; Zhang, Qiang; ...

  17. Rigidifying Fluorescent Linkers by Metal-Organic Framework Formation...

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    Rigidifying Fluorescent Linkers by Metal-Organic Framework Formation for Fluorescence Blue Shift and Quantum Yield Enhancement Previous Next List Zhangwen Wei, Zhi-Yuan Gu, Ravi K. ...

  18. Size-Controlled Synthesis of Porphyrinic Metal-Organic Framework...

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    Size-Controlled Synthesis of Porphyrinic Metal-Organic Framework and Functionalization for Targeted Photodynamic Therapy Previous Next List Jiang, Juncong; Zhao, Yingbo; and Yaghi, ...

  19. Piezofluorochromic Metal-Organic Framework: A Microscissor Lift...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Piezofluorochromic Metal-Organic Framework: A Microscissor Lift Previous Next List Zhang, Qiang; Su, Jie; Feng, Dawei; Wei, Zhangwen; Zou, Xiaodong; Zhou, Hong-Cai. ...

  20. Pyrazolate-Based Porphyrinic Metal-Organic Framework with Extraordinar...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Pyrazolate-Based Porphyrinic Metal-Organic Framework with Extraordinary Base-Resistance Previous Next List Wang, Kecheng; Lv, Xiu-Liang; Feng, Dawei; Li, Jian; Chen, Shuangming; ...

  1. Photochromic Metal-Organic Frameworks: Reversible Control of...

    Office of Scientific and Technical Information (OSTI)

    Reversible Control of Singlet Oxygen Generation Citation Details In-Document Search Title: Photochromic Metal-Organic Frameworks: Reversible Control of Singlet Oxygen ...

  2. Rational design of metal-organic frameworks with anticipated...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Rational design of metal-organic frameworks with anticipated porosities and ... Until now, much progress has been made to rationalize the design and synthesis of MOFs. ...

  3. Piezofluorochromic Metal-Organic Framework: A Microscissor Lift...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Piezofluorochromic Metal-Organic Framework: A Microscissor Lift Previous Next List Zhang, Qiang; Su, Jie; Feng, Dawei; Wei, Zhangwen; Zou, Xiaodong; Zhou, Hong-Cai....

  4. High Methane Storage Capacity in Aluminum Metal-Organic Frameworks...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    High Methane Storage Capacity in Aluminum Metal-Organic Frameworks Previous Next List Felipe Gndara, Hiroyasu Furukawa, Seungkyu Lee, and Omar M. Yaghi, J. Am. Chem. Soc., 136,...

  5. Stable metal-organic frameworks containing single-molecule traps...

    Office of Scientific and Technical Information (OSTI)

    Title: Stable metal-organic frameworks containing single-molecule traps for enzyme encapsulation Authors: Feng, Dawei ; Liu, Tian-Fu ; Su, Jie ; Bosch, Mathieu ; Wei, Zhangwen ; ...

  6. The Chemistry and Applications of Metal-Organic Frameworks |...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Chemistry and Applications of Metal-Organic Frameworks Previous Next List Hiroyasu Furukawa, Kyle E. Cordova, Michael O'Keeffe, Omar M. Yaghi, Science, 341, 1230444 (2013) DOI:...

  7. Mapping of Functional Groups in Metal-Organic Frameworks | Center...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Mapping of Functional Groups in Metal-Organic Frameworks Previous Next List Xueqian Kong, Hexiang Deng, Fangyong Yan, Jihan Kim, Joseph A. Swisher, Berend Smit, Omar M. Yaghi,...

  8. A Single Crystalline Porphyrinic Titanium Metal-Organic Framework...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Single Crystalline Porphyrinic Titanium Metal-Organic Framework Previous Next List Yuan, Shuai; Liu, Tian-Fu; Feng, Dawei; Tian, Jian; Wang, Kecheng; Qin, Junsheng; Zhang, Qiang;...

  9. Sandia Energy - Sandia Metal-Organic Framework LDRD Research...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Technology (NIST) collaborators, published "Tunable electrical conductivity in metal-organic framework thin-film devices" in the December 5 edition of Science. The paper reports...

  10. Selective Gas Adsorption in the Flexible Metal-Organic Frameworks...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Selective Gas Adsorption in the Flexible Metal-Organic Frameworks Cu(BDTri)L (L DMF, DEF) ... that design of a flexible framework cavity can control the pore opening ...

  11. Synthesis and Characterization of Metal-Organic Framework-74...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Synthesis and Characterization of Metal-Organic Framework-74 Containing 2, 4, 6, 8, and 10 Different Metals Previous Next List Lisa J. Wang, Hexiang Deng, Hiroyasu Furukawa, Felipe ...

  12. Introduction of Functionalized Mesopores to Metal-Organic Frameworks...

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    Introduction of Functionalized Mesopores to Metal-Organic Frameworks via Metal-Ligand-Fragment Coassembly Previous Next List Jinhee Park, Zhiyong U. Wang, Lin-Bing Sun, Ying-Pin...

  13. Luminescent metal-organic frameworks (MOFs); a nanolaboratory for

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    photophysics | MIT-Harvard Center for Excitonics Luminescent metal-organic frameworks (MOFs); a nanolaboratory for photophysics February 7, 2012 at 3pm/36-428 Mark Allendorf Sandia National Laboratories allendorf001_000 Abstract: Metal-organic frameworks (MOFs) are a diverse class of crystalline supramolecular materials characterized by rigid, nanoporous structures and an exceptional level of synthetic versatility. Since the organic component of MOFs, referred to as the "linker,"

  14. Crystalline Microporous Metal-Organic Frameworks: Opportunities in Energy

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Research | MIT-Harvard Center for Excitonics Crystalline Microporous Metal-Organic Frameworks: Opportunities in Energy Research April 26, 2011 at 3pm/38-401A Mircea Dinca Department of Chemistry, Massachusetts Institute of Technology dinca abstract: Metal-organic frameworks (MOFs) are crystalline solids wherein inorganic nodes are connected by organic ligands to give rise to highly ordered and monodisperse micropores with diameters ranging from 0.5 to ~ 2 nanometers. The micropores are

  15. Metal-Organic Frameworks as Biomimetic Catalysts | Center for...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Abstract: In this Minireview, we have summarized the recent progress of biomimetic catalysis in the field of metal-organic frameworks (MOFs) with a focus on the implantation of...

  16. Hydrocarbon Separations in a Metal-Organic Framework with Open...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Hydrocarbon Separations in a Metal-Organic Framework with Open Iron(II) Coordination Sites Previous Next List E. D. Bloch, W. L. Queen, R. Krishna, J. M. Zadrozny, C. M. Brown, and ...

  17. A porous metal-organic framework with helical chain building...

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    porous metal-organic framework with helical chain building units exhibiting facile transition from micro- to meso-porosity Previous Next List Jinhee Park , Jian-Rong Li , E. ...

  18. A versatile metal-organic framework for carbon dioxide capture...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    versatile metal-organic framework for carbon dioxide capture and cooperative catalysis Previous Next List Jinhee Park, Jian-Rong Li, Ying-Pin Chen, Jiamei Yu, Andrey A. Yakovenko, ...

  19. A Highly Stable Porphyrinic Zirconium Metal-Organic Framework...

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    Highly Stable Porphyrinic Zirconium Metal-Organic Framework with shp-a Topology Previous Next List Dawei Feng, Zhi-Yuan Gu, Ying-Pin Chen, Jihye Park, Zhangwen Wei, Yujia Sun, ...

  20. Transparent Metal-Organic Framework/Polymer Mixed Matrix Membranes...

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    Transparent Metal-Organic FrameworkPolymer Mixed Matrix Membranes as Water Vapor Barriers Previous Next List Bae, Youn Jue; Cho, Eun Seon; Qu, Fen; Sun, Daniel T.; Williams, ...

  1. An Exceptionally Stable, Porphyrinic Zr Metal-Organic Framework...

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    An Exceptionally Stable, Porphyrinic Zr Metal-Organic Framework Exhibiting pH-Dependent Fluorescence Previous Next List Hai-Long Jiang, Dawei Feng, Kecheng Wang, Zhi-Yuan Gu, ...

  2. Probing Adsorption Interactions In Metal-Organic Framework Using...

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    Probing Adsorption Interactions In Metal-Organic Framework Using X-ray Spectroscopy Previous Next List Walter S. Drisdell, Roberta Poloni, Thomas M. McDonald, Jeffrey R. Long, ...

  3. "Heterogeneity within Order" in Metal-Organic Frameworks | Center...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    within Order" in Metal-Organic Frameworks Previous Next List Hiroyasu Furukawa, Ulrich Mller and Omar M. Yaghi, Angew. Chem. Int. Ed. 54, 3417-3430 (2015) DOI: 10.1002...

  4. Ultrastable Polymolybdate-Based Metal-Organic Frameworks as Highly...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Metal-Organic Frameworks as Highly Active Electrocatalysts for Hydrogen Generation from Water Previous Next List Qin, Jun-Sheng; Du, Dong-Ying; Guan, Wei; Bo, Xiang-Jie; Li,...

  5. Stable Metal-Organic Frameworks Containing Single-Molecule Traps...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Stable Metal-Organic Frameworks Containing Single-Molecule Traps for Enzyme Encapsulation Previous Next List Dawei Feng, Tian-Fu Liu, Jie Su, Mathieu Bosch, Zhangwen Wei, Wei Wan,...

  6. Increasing the Stability of Metal-Organic Frameworks (Journal...

    Office of Scientific and Technical Information (OSTI)

    Citation Details In-Document Search Title: Increasing the Stability of Metal-Organic Frameworks Authors: Bosch, Mathieu ; Zhang, Muwei ; Zhou, Hong-Cai Publication Date: 2014-01-01 ...

  7. Hydrocarbon Separations in Metal-Organic Frameworks | Center...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Hydrocarbon Separations in Metal-Organic Frameworks Previous Next List Zoey R. Herm, Eric D. Bloch, and Jeffrey R. Long, Chem. Mater., 26 (1), pp 323-338 (2014) DOI: 10.1021...

  8. Brnsted Acidity in Metal-Organic Frameworks | Center for Gas...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    List Jiang, Juncong and Yaghi, Omar, M. Bronsted Acidity in Metal-Organic Frameworks. Chem. Rev., 115, 6966-6997 (2015). DOI: 10.1021acs.chemrev.5b00221 Bronsted Acidity in MOFs...

  9. Functional Mesoporous Metal-Organic Frameworks for the Capture...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    mesoporous metal-organic frameworks (MOFs) with cavities up to 2.73 nm, designated as PCN-100 and PCN-101 (PCN represents porous coordination network), have been synthesized. N2...

  10. Protein Immobilization in Metal-Organic Frameworks by Covalent...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Protein Immobilization in Metal-Organic Frameworks by Covalent Binding Previous Next List Xuan Wang, Trevor A. Makal and Hong-Cai Zhou, Aust. J. Chem. 67, 1629-1631 (2014) DOI:...

  11. Screening Metal-Organic Frameworks by Analysis of Transient Breakthrou...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Screening Metal-Organic Frameworks by Analysis of Transient Breakthrough of Gas Mixtures in a Fixed Bed Adsorber Previous Next List Rajamani Krishna and Jeffrey R. Long, J. Phys....

  12. Carbon Dioxide Capture in Metal-Organic Frameworks | Center for...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Carbon Dioxide Capture in Metal-Organic Frameworks Previous Next List Kenji Sumida , David L. Rogow , Jarad A. Mason , Thomas M. McDonald , Eric D. Bloch , Zoey R. Herm , Tae-Hyun...

  13. Water Adsorption in Porous Metal-Organic Frameworks and Related...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Water Adsorption in Porous Metal-Organic Frameworks and Related Materials Previous Next ... Soc., 136, 4369-4381 (2014) DOI: 10.1021ja500330a Abstract Image Abstract: Water ...

  14. Omar Yaghi on Chemistry and Metal Organic Frameworks

    SciTech Connect (OSTI)

    Omar Yaghi

    2012-07-23

    In this edited version of the hour long talk, Omar Yaghi, director of the Molecular Foundry, sat down in conversation with Jeff Miller, head of Public Affairs, on July 11th, 2012 to discuss his fascination with the hidden world of chemistry and his work on Metal Organic Frameworks.

  15. Omar Yaghi on Chemistry and Metal Organic Frameworks

    ScienceCinema (OSTI)

    Omar Yaghi

    2013-06-24

    In this edited version of the hour long talk, Omar Yaghi, director of the Molecular Foundry, sat down in conversation with Jeff Miller, head of Public Affairs, on July 11th, 2012 to discuss his fascination with the hidden world of chemistry and his work on Metal Organic Frameworks.

  16. Metal-Organic Frameworks for Highly Selective Separations

    SciTech Connect (OSTI)

    Omar M. Yaghi

    2009-09-28

    This grant was focused on the study of metal-organic frameworks with these specific objectives. (1) To examine the use of MOFs with well-defined open metal sites for binding of gases and small organics. (2) To develop a strategy for producing MOFs that combine large pore size with high surface area for their use in gas adsorption and separation of polycyclic organic compounds. (3) To functionalize MOFs for the storage of inert gases such as methane. A brief outline of our progress towards these objectives is presented here as it forms part of the basis for the ideas to be developed under the present proposal.

  17. CO2 Dynamics in a Metal-Organic Framework with Open Metal Sites...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Dynamics in a Metal-Organic Framework with Open Metal Sites Previous Next List Xueqian Kong, Eric Scott, Wen Ding, Jarad A. Mason, Jeffrey R. Long, and Jeffrey A. Reimer, J. Am. ...

  18. Water Adsorption in Metal-Organic Frameworks with Open-Metal...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Water Adsorption in Metal-Organic Frameworks with Open-Metal Sites Previous Next List Xuan Peng, Li-Chiang Lin, Weizhen Sun and Berend Smit, AIChe J. 6, 677-687 (2015) DOI:...

  19. Increasing the Stability of Metal-Organic Frameworks

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Bosch, Mathieu; Zhang, Muwei; Zhou, Hong-Cai

    2014-01-01

    Metal-organic frameworks (MOFs) are a new category of advanced porous materials undergoing study by many researchers for their vast variety of both novel structures and potentially useful properties arising from them. Their high porosities, tunable structures, and convenient process of introducing both customizable functional groups and unsaturated metal centers have afforded excellent gas sorption and separation ability, catalytic activity, luminescent properties, and more. However, the robustness and reactivity of a given framework are largely dependent on its metal-ligand interactions, where the metal-containing clusters are often vulnerable to ligand substitution by water or other nucleophiles, meaning that the frameworks may collapsemore » upon exposure even to moist air. Other frameworks may collapse upon thermal or vacuum treatment or simply over time. This instability limits the practical uses of many MOFs. In order to further enhance the stability of the framework, many different approaches, such as the utilization of high-valence metal ions or nitrogen-donor ligands, were recently investigated. This review details the efforts of both our research group and others to synthesize MOFs possessing drastically increased chemical and thermal stability, in addition to exemplary performance for catalysis, gas sorption, and separation.« less

  20. Ligand-Assisted Enhancement of CO2 Capture in Metal-Organic Frameworks...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Ligand-Assisted Enhancement of CO2 Capture in Metal-Organic Frameworks Previous Next List R. ... to a novel "BTT-type" metal-organic framework (MOF) featuring open metal centers. ...

  1. A single crystalline porphyrinic titanium metalorganic framework

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Yuan, Shuai; Liu, Tian -Fu; Feng, Dawei; Tian, Jian; Wang, Kecheng; Qin, Junsheng; Zhang, Qiang; Chen, Ying -Pin; Bosch, Mathieu; Zou, Lanfang; et al

    2015-04-28

    We successfully assembled the photocatalytic titanium-oxo cluster and photosensitizing porphyrinic linker into a metalorganic framework (MOF), namely PCN-22. A preformed titanium-oxo carboxylate cluster is adopted as the starting material to judiciously control the MOF growth process to afford single crystals. This synthetic method is useful to obtain highly crystalline titanium MOFs, which has been a daunting challenge in this field. Moreover, PCN-22 demonstrated permanent porosity and photocatalytic activities toward alcohol oxidation.

  2. Evaluating metal-organic frameworks for natural gas storage

    SciTech Connect (OSTI)

    Mason, JA; Veenstra, M; Long, JR

    2014-01-01

    Metal-organic frameworks have received significant attention as a new class of adsorbents for natural gas storage; however, inconsistencies in reporting high-pressure adsorption data and a lack of comparative studies have made it challenging to evaluate both new and existing materials. Here, we briefly discuss high-pressure adsorption measurements and review efforts to develop metal-organic frameworks with high methane storage capacities. To illustrate the most important properties for evaluating adsorbents for natural gas storage and for designing a next generation of improved materials, six metal-organic frameworks and an activated carbon, with a range of surface areas, pore structures, and surface chemistries representative of the most promising adsorbents for methane storage, are evaluated in detail. High-pressure methane adsorption isotherms are used to compare gravimetric and volumetric capacities, isosteric heats of adsorption, and usable storage capacities. Additionally, the relative importance of increasing volumetric capacity, rather than gravimetric capacity, for extending the driving range of natural gas vehicles is highlighted. Other important systems-level factors, such as thermal management, mechanical properties, and the effects of impurities, are also considered, and potential materials synthesis contributions to improving performance in a complete adsorbed natural gas system are discussed.

  3. L-Aspartate Links for Stable Sodium Metal-Organic Frameworks...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    L-Aspartate Links for Stable Sodium Metal-Organic Frameworks Previous Next List Siman, Peter; ... linker with flexible carboxylate groups to enhance framework stability. ...

  4. Stimuli-Responsive Metal Organic Frameworks: Stimuli-Responsive Metal Organic Frameworks for Energy-Efficient Post Combustion Capture

    SciTech Connect (OSTI)

    2010-07-01

    IMPACCT Project: A team led by three professors at Texas A&M is developing a subset of metal organic frameworks that respond to stimuli such as small changes in temperature to trap CO2 and then release it for storage. These frameworks are a promising class of materials for carbon capture applications because their structure and chemistry can be controlled with great precision. Because the changes in temperature required to trap and release CO2 in Texas A&M’s frameworks are much smaller than in other carbon capture approaches, the amount of energy or stimulus that has to be diverted from coal-fired power plants to accomplish this is greatly reduced. The team is working to alter the materials so they bind only with CO2, and are stable enough to withstand the high temperatures found in the chimneys of coal-fired power plants.

  5. Metal-organic frameworks for Xe/Kr separation

    SciTech Connect (OSTI)

    Ryan, Patrick J.; Farha, Omar K.; Broadbelt, Linda J.; Snurr, Randall Q.; Bae, Youn-Sang

    2013-08-27

    Metal-organic framework (MOF) materials are provided and are selectively adsorbent to xenon (Xe) over another noble gas such as krypton (Kr) and/or argon (Ar) as a result of having framework voids (pores) sized to this end. MOF materials having pores that are capable of accommodating a Xe atom but have a small enough pore size to receive no more than one Xe atom are desired to preferentially adsorb Xe over Kr in a multi-component (Xe--Kr mixture) adsorption method. The MOF material has 20% or more, preferably 40% or more, of the total pore volume in a pore size range of 0.45-0.75 nm which can selectively adsorb Xe over Kr in a multi-component Xe--Kr mixture over a pressure range of 0.01 to 1.0 MPa.

  6. Metal-organic frameworks for Xe/Kr separation

    SciTech Connect (OSTI)

    Ryan, Patrick J.; Farha, Omar K.; Broadbelt, Linda J.; Snurr, Randall Q.; Bae, Youn-Sang

    2014-07-22

    Metal-organic framework (MOF) materials are provided and are selectively adsorbent to xenon (Xe) over another noble gas such as krypton (Kr) and/or argon (Ar) as a result of having framework voids (pores) sized to this end. MOF materials having pores that are capable of accommodating a Xe atom but have a small enough pore size to receive no more than one Xe atom are desired to preferentially adsorb Xe over Kr in a multi-component (Xe--Kr mixture) adsorption method. The MOF material has 20% or more, preferably 40% or more, of the total pore volume in a pore size range of 0.45-0.75 nm which can selectively adsorb Xe over Kr in a multi-component Xe--Kr mixture over a pressure range of 0.01 to 1.0 MPa.

  7. Understanding Trends in CO2 adsorption in Metal-Organic Frameworks...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Understanding Trends in CO2 adsorption in Metal-Organic Frameworks with Open-Metal Sites ... bond analysis, we study and explain trends in the binding between CO2 and open-metal ...

  8. Robust Metal-Organic Framework with An Octatopic Ligand for Gas...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Robust Metal-Organic Framework with An Octatopic Ligand for Gas Adsorption and Separation: Combined Characterization by Experiments and Molecular Simulation Previous Next List ...

  9. Novel Metal-Organic Frameworks | Center for Gas SeparationsRelevant...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Novel Metal-Organic Frameworks Previous Next List Close Jeffrey Long Omar Yaghi Omar Yaghi Hongcai (Joe) Zhou Hong-Cai (Joe) Zhou...

  10. Small Molecule Adsorption in Open-Site Metal-Organic Frameworks...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Small Molecule Adsorption in Open-Site Metal-Organic Frameworks: A Systematic Density Functional Theory Study for Rational Design Previous Next List Kyuho Lee, Joshua D. Howe,...

  11. High-Throughput Methodology for Discovery of Metal-Organic Frameworks...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Methodology for Discovery of Metal-Organic Frameworks with a High Hydrogen Binding Enthalpy Steven S. Kaye, Satoshi Horike, and Jeffrey R. Long Department of Chemistry, University ...

  12. Metal-organic frameworks for lithium ion batteries and supercapacitors

    SciTech Connect (OSTI)

    Ke, Fu-Sheng; Wu, Yu-Shan; Deng, Hexiang

    2015-03-15

    Porous materials have been widely used in batteries and supercapacitors attribute to their large internal surface area (usually 100–1000 m{sup 2} g{sup −1}) and porosity that can favor the electrochemical reaction, interfacial charge transport, and provide short diffusion paths for ions. As a new type of porous crystalline materials, metal-organic frameworks (MOFs) have received huge attention in the past decade due to their unique properties, i.e. huge surface area (up to 7000 m{sup 2} g{sup −1}), high porosity, low density, controllable structure and tunable pore size. A wide range of applications including gas separation, storage, catalysis, and drug delivery benefit from the recent fast development of MOFs. However, their potential in electrochemical energy storage has not been fully revealed. Herein, the present mini review appraises recent and significant development of MOFs and MOF-derived materials for rechargeable lithium ion batteries and supercapacitors, to give a glimpse into these potential applications of MOFs. - Graphical abstract: MOFs with large surface area and high porosity can offer more reaction sites and charge carriers diffusion path. Thus MOFs are used as cathode, anode, electrolyte, matrix and precursor materials for lithium ion battery, and also as electrode and precursor materials for supercapacitors. - Highlights: • MOFs have potential in electrochemical area due to their high porosity and diversity. • We summarized and compared works on MOFs for lithium ion battery and supercapacitor. • We pointed out critical challenges and provided possible solutions for future study.

  13. Understanding CO2 Dynamics in Metal-Organic Frameworks wit Open...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    CO2 Dynamics in Metal-Organic Frameworks wit Open Metal Sites Previous Next List Li-Chiang Lin, Jihan Kim, Xueqian Kong, Eric Scott, Thomas M. McDonald, Jeffrey R. Long, Jeffrey A....

  14. Metal-organic framework materials based on icosahedral boranes and carboranes

    DOE Patents [OSTI]

    Mirkin, Chad A.; Hupp, Joseph T.; Farha, Omar K.; Spokoyny, Alexander M.; Mulfort, Karen L.

    2010-11-02

    Disclosed herein are metal-organic frameworks of metals and boron rich ligands, such as carboranes and icosahedral boranes. Methods of synthesizing and using these materials in gas uptake are disclosed.

  15. Tunable electrical conductivity in metal-organic framework thin film devices

    DOE Patents [OSTI]

    Talin, Albert Alec; Allendorf, Mark D.; Stavila, Vitalie; Leonard, Francois

    2016-05-24

    A composition including a porous metal organic framework (MOF) including an open metal site and a guest species capable of charge transfer that can coordinate with the open metal site, wherein the composition is electrically conductive. A method including infiltrating a porous metal organic framework (MOF) including an open metal site with a guest species that is capable of charge transfer; and coordinating the guest species to the open metal site to form a composition including an electrical conductivity greater than an electrical conductivity of the MOF.

  16. Carbon Dioxide Separation with Novel Microporous Metal Organic Frameworks

    SciTech Connect (OSTI)

    Richard Willis; Annabelle Benin; John Low; Ganesh Venimadhavan; Syed Faheem; David Lesch; Adam Matzger; Randy Snurr

    2008-02-04

    The goal of this program was to develop a low cost novel sorbent to remove carbon dioxide from flue gas and gasification streams in electric utilities. Porous materials named metal-organic frameworks (MOFs) were found to have good capacity and selectivity for the capture of carbon dioxide. Several materials from the initial set of reference MOFs showed extremely high CO{sub 2} adsorption capacities and very desirable linear isotherm shapes. Sample preparation occurred at a high level, with a new family of materials suitable for intellectual property protection prepared and characterized. Raman spectroscopy was shown to be useful for the facile characterization of MOF materials during adsorption and especially, desorption. Further, the development of a Raman spectroscopic-based method of determining binary adsorption isotherms was initiated. It was discovered that a stronger base functionality will need to be added to MOF linkers in order to enhance CO{sub 2} selectivity over other gases via a chemisorption mechanism. A concentrated effort was expended on being able to accurately predict CO{sub 2} selectivities and on the calculation of predicted MOF surface area values from first principles. A method of modeling hydrolysis on MOF materials that correlates with experimental data was developed and refined. Complimentary experimental data were recorded via utilization of a combinatorial chemistry heat treatment unit and high-throughput X-ray diffractometer. The three main Deliverables for the project, namely (a) a MOF for pre-combustion (e.g., IGCC) CO{sub 2} capture, (b) a MOF for post-combustion (flue gas) CO{sub 2} capture, and (c) an assessment of commercial potential for a MOF in the IGCC application, were completed. The key properties for MOFs to work in this application - high CO{sub 2} capacity, good adsorption/desorption rates, high adsorption selectivity for CO{sub 2} over other gases such as methane and nitrogen, high stability to contaminants, namely

  17. Methods for associating or dissociating guest materials with a metal organic framework, systems for associating or dissociating guest materials within a series of metal organic frameworks, thermal energy transfer assemblies, and methods for transferring thermal energy

    DOE Patents [OSTI]

    McGrail, B. Peter; Brown, Daryl R.; Thallapally, Praveen K.

    2016-08-02

    Methods for releasing associated guest materials from a metal organic framework are provided. Methods for associating guest materials with a metal organic framework are also provided. Methods are provided for selectively associating or dissociating guest materials with a metal organic framework. Systems for associating or dissociating guest materials within a series of metal organic frameworks are provided. Thermal energy transfer assemblies are provided. Methods for transferring thermal energy are also provided.

  18. Methods for associating or dissociating guest materials with a metal organic framework, systems for associating or dissociating guest materials within a series of metal organic frameworks, thermal energy transfer assemblies, and methods for transferring thermal energy

    DOE Patents [OSTI]

    McGrail, B. Peter; Brown, Daryl R.; Thallapally, Praveen K.

    2014-08-05

    Methods for releasing associated guest materials from a metal organic framework are provided. Methods for associating guest materials with a metal organic framework are also provided. Methods are provided for selectively associating or dissociating guest materials with a metal organic framework. Systems for associating or dissociating guest materials within a series of metal organic frameworks are provided. Thermal energy transfer assemblies are provided. Methods for transferring thermal energy are also provided.

  19. Separation of Hexane Isomers in a Metal-Organic Framework with...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Separation of Hexane Isomers in a Metal-Organic Framework with Triangular Channels Previous Next List Zoey R. Herm, Brian M. Wiers, Jarad A. Mason, Jasper M. van Baten, Matthew R. ...

  20. Tetratopic phenyl compounds, related metal-organic framework materials and post-assembly elaboration

    SciTech Connect (OSTI)

    Farha, Omar K.; Hupp, Joseph T.

    2012-09-11

    Disclosed are tetratopic carboxylic acid phenyl for use in metal-organic framework compounds. These compounds are useful in catalysis, gas storage, sensing, biological imaging, drug delivery and gas adsorption separation.

  1. Stepwise adsorption in a mesoporous metal-organic framework: experimental and computational analysis

    SciTech Connect (OSTI)

    Yuan, Daqiang; Getman, Rachel B; Wei, Zhangwen; Snurr, Randall Q; Zhou, Hong-Cai

    2012-04-02

    Stepwise adsorption in a metal-organic framework with both micro- and meso-pores is caused by adsorbates first filling the micropores, then adsorbing along the mesopore walls, and finally filling the mesopores.

  2. A Highly Porous and Robust (3,3,4)-Connected Metal-Organic Framework...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Highly Porous and Robust (3,3,4)-Connected Metal-Organic Framework Assembled with a 90 Bridging-Angle Embedded Octacarboxylate Ligand Previous Next List Weigang Lu, Daqiang Yuan, ...

  3. Tetratopic phenyl compounds, related metal-organic framework materials and post-assembly elaboration

    SciTech Connect (OSTI)

    Farha, Omar K; Hupp, Joseph T

    2013-06-25

    Disclosed are tetratopic carboxylic acid phenyl for use in metal-organic framework compounds. These compounds are useful in catalysis, gas storage, sensing, biological imaging, drug delivery and gas adsorption separation.

  4. Ab-initio Carbon Capture in Open-Site Metal Organic Frameworks...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Ab-initio Carbon Capture in Open-Site Metal Organic Frameworks Previous Next List A. ... of CO2 in open-site Mg-MOF-74, which has emerged as a promising MOF for CO2 capture. ...

  5. Metal-Organic Frameworks Based on Previously Unknown Zr8/Hf Cubic...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Metal-Organic Frameworks Based on Previously Unknown Zr8Hf Cubic Clusters Previous Next List Dawei Feng, Hai-Long Jiang, Ying-Pin Chen, Zhi-Yuan Gu, Zhangwen Wei, and Hong-Cai...

  6. Metal-Organic Frameworks for Separations | Center for GasSeparationsR...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Metal-Organic Frameworks for Separations Previous Next List Jian-Rong Li , Julian Sculley , and Hong-Cai Zhou, Chem. Rev., 2012, 112 (2), pp 869-932 DOI: 10.1021cr200190s Journal...

  7. Rapidly assessing the activation conditions and porosity of metal-organic frameworks using thermogravimetric analysis

    SciTech Connect (OSTI)

    McDonald, TM; Bloch, ED; Long, JR

    2015-01-01

    A methodology utilizing a thermogravimetric analyzer to monitor propane uptake following incremental increases of the temperature is demonstrated as a means of rapidly identifying porous materials and determining the optimum activation conditions of metal-organic frameworks.

  8. Symmetry-Guided Synthesis of Highly Porous Metal-Organic Frameworks...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Symmetry-Guided Synthesis of Highly Porous Metal-Organic Frameworks with Fluorite Topology Previous Next List Muwei Zhang, Ying-Pin Chen, Mathieu Bosch, Thomas Gentle III, Kecheng...

  9. Multirate delivery of multiple therapeutic agents from metal-organic frameworks

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    McKinlay, Alistair C.; Allan, Phoebe K.; Renouf, Catherine L.; Duncan, Morven J.; Wheatley, Paul S.; Warrender, Stewart J.; Dawson, Daniel; Ashbrook, Sharon E.; Gil, Barbara; Marszalek, Bartosz; et al

    2014-12-01

    The highly porous nature of metal-organic frameworks (MOFs) offers great potential for the delivery of therapeutic agents. Here, we show that highly porous metal-organic frameworks can be used to deliver multiple therapeutic agents—a biologically active gas, an antibiotic drug molecule, and an active metal ion—simultaneously but at different rates. The possibilities offered by delivery of multiple agents with different mechanisms of action and, in particular, variable timescales may allow new therapy approaches. Here, we show that the loaded MOFs are highly active against various strains of bacteria.

  10. Multirate delivery of multiple therapeutic agents from metal-organic frameworks

    SciTech Connect (OSTI)

    McKinlay, Alistair C.; Allan, Phoebe K.; Renouf, Catherine L.; Duncan, Morven J.; Wheatley, Paul S.; Warrender, Stewart J.; Dawson, Daniel; Ashbrook, Sharon E.; Gil, Barbara; Marszalek, Bartosz; Dren, Tina; Williams, Jennifer J.; Charrier, Cedric; Mercer, Derry K.; Teat, Simon J.; Morris, Russell E.

    2014-12-01

    The highly porous nature of metal-organic frameworks (MOFs) offers great potential for the delivery of therapeutic agents. Here, we show that highly porous metal-organic frameworks can be used to deliver multiple therapeutic agentsa biologically active gas, an antibiotic drug molecule, and an active metal ionsimultaneously but at different rates. The possibilities offered by delivery of multiple agents with different mechanisms of action and, in particular, variable timescales may allow new therapy approaches. Here, we show that the loaded MOFs are highly active against various strains of bacteria.

  11. When Metal Organic Frameworks Turn into One-Dimensional Magnets...

    Office of Science (SC) Website

    Contact Information Basic Energy Sciences U.S. Department of Energy SC-22Germantown ... one-dimensional chains of transition metal magnets (green sections of structure). ...

  12. Construction of Ultrastable Porphyrin Zr Metal-Organic Frameworks...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    A series of highly stable MOFs with 3-D nanochannels, namely PCN-224 (no metal, Ni, Co, Fe), have been assembled with six-connected Zr6 cluster and metalloporphyrins by a...

  13. Metal Insertion in a Microporous Metal-Organic Framework Lined with 2,2'-Bipyridine

    SciTech Connect (OSTI)

    Bloch, Eric D.; Britt, David; Lee, Chain; Doonan, Christian J.; Uribe-Romo, Fernando J.; Furukawa, Hiroyasu; Long, Jeffrey R.; Yaghi, Omar M.

    2010-10-20

    Reaction of AlCl3·6H2O with 2,2'-bipyridine-5,5'-dicarboxylic acid (H2bpydc) affords Al(OH)(bpydc) (1, MOF-253), the first metal-organic framework with open 2,2'-bipyridine (bpy) coordination sites. The material displays a BET surface area of 2160 m2/g and readily complexes metals to afford, for example, 1·xPdCl2 (x = 0.08, 0.83) and 1·0.97Cu(BF4)2. EXAFS spectroscopy performed on 1·0.83PdCl2 reveals the expected square planar coordination geometry, matching the structure of the model complex (bpy)PdCl2. Finally, significantly, the selectivity factor for binding CO2 over N2 under typical flue gas conditions is observed to increase from 2.8 in 1 to 12 in 1·0.97Cu(BF4)2.

  14. Synthesis and Characterization of Metal–Organic Framework-74 Containing 2, 4, 6, 8, and 10 Different Metals

    SciTech Connect (OSTI)

    Wang, Lisa J.; Deng, Hexiang; Furukawa, Hiroyasu; Gándara, Felipe; Cordova, Kyle E.; Peri, Dani; Yaghi, Omar M.

    2014-06-16

    Metal–organic frameworks (MOFs) containing more than two types of metal ions mixed within one secondary building unit are studied.

  15. A nanotubular metal-organic framework with permanent porosity : structure analysis and gas sorption studies.

    SciTech Connect (OSTI)

    Ma, S.; Simmons, J. M.; Li, J. R.; Yuan, D.; Weng, W.; Liu, D. J.; Zhou, H. C.; Chemical Sciences and Engineering Division; Texas A&M Univ.; NIST

    2009-01-01

    A nanotubular metal-organic framework, PCN-19, was constructed based on a micro3-oxo-trinickel basic carboxylate secondary building unit (SBU) and the 9,10-anthracenedicarboxylate ligand; its permanent porosity was confirmed by N2 adsorption isotherms, and its H2 storage performances were evaluated under both low and high pressures at 77 K.

  16. Nickel(II) and Copper(I,II)-based Metal-Organic Frameworks Incorporati...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    nickel(II) perchlorate or copper(II) nitrate afforded two new metal-organic frameworks, Ni3(BTPP)2solvent (Ni-BTPP) and CuI4CuII2(OH)2(BTPP)2 solvent (Cu-BTPP). Powder...

  17. Heterogeneity of functional groups in a metal-organic framework displays magic number ratios

    SciTech Connect (OSTI)

    Sue, Andrew C.-H.; Mannige, Ranjan V.; Deng, Hexiang; Cao, Dennis; Wang, Cheng; Gándara, Felipe; Stoddart, J. Fraser; Whitelam, Stephen; Yaghi, Omar M.

    2015-05-20

    Multiple organic functionalities can now be apportioned into nanoscale domains within a metal-coordinated framework, posing the following question: how do we control the resulting combination of “heterogeneity and order”? Here, we report the creation of a metal–organic framework, MOF-2000, whose two component types are incorporated in a 2:1 ratio, even when the ratio of component types in the starting solution is varied by an order of magnitude. Statistical mechanical modeling suggests that this robust 2:1 ratio has a nonequilibrium origin, resulting from kinetic trapping of component types during framework growth. Our simulations show how other “magic number” ratios of components can be obtained by modulating the topology of a framework and the noncovalent interactions between component types, a finding that may aid the rational design of functional multicomponent materials.

  18. Separation of polar compounds using a flexible metal-organic framework

    SciTech Connect (OSTI)

    Motkuri, Radha K.; Thallapally, Praveen K.; Annapureddy, Harsha V.; Dang, Liem X.; Krishna, Rajamani; Nune, Satish K.; Fernandez, Carlos A.; Liu, Jian; McGrail, B. Peter

    2015-01-01

    A flexible metal-organic framework constructed from a flexible linker is shown to possess the capability of separating mixtures of polar compounds by exploiting the differences in the saturation capacities of the constituents. The separation possibilities with the flexible MOF include mixtures of propanol isomers, and various azeotropes. Transient breakthrough simulations show that these sorption-based separations are in favor of the component with higher saturation capacity.

  19. Zeolite-like metalorganic frameworks (ZMOFs): Design, synthesis, and properties

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Eddaoudi, Mohamed; Sava, Dorina F.; Eubank, Jarrod F.; Adil, Karim; Guillerm, Vincent

    2015-10-24

    This study highlights various design and synthesis approaches toward the construction of ZMOFs, which are metalorganic frameworks (MOFs) with topologies and, in some cases, features akin to traditional inorganic zeolites. The interest in this unique subset of MOFs is correlated with their exceptional characteristics arising from the periodic pore systems and distinctive cage-like cavities, in conjunction with modular intra- and/or extra-framework components, which ultimately allow for tailoring of the pore size, pore shape, and properties towards specific applications.

  20. Computational studies of adsorption in metal organic frameworks and interaction of nanoparticles in condensed phases

    SciTech Connect (OSTI)

    Annapureddy, Harsha V.; Motkuri, Radha K.; Nguyen, Phuong T.; Truong, T. B.; Thallapally, Praveen K.; McGrail, B. Peter; Dang, Liem X.

    2014-01-08

    In this review, we describe recent efforts in which computer simulations were used to systematically study nano-structured metal organic frameworks, with particular emphasis on their application in heating and cooling processes. These materials also are known as metal organic heat carriers. We used both molecular dynamics and Grand Canonical Monte Carlo simulation techniques to gain a molecular-level understanding of the adsorption mechanism of gases in these porous materials. We investigated the uptake of various gases such as refrigerants R12 and R143a and also the elemental gases Xe and Rn by the metal organic framework (i.e., Ni2(dhtp)). We also evaluated the effects of temperature and pressure on the uptake mechanism. Our computed results compared reasonably well with available experimental measurements, thus validating our potential models and approaches. In addition, we also investigated the structural, diffusive, and adsorption properties of different hydrocarbons in Ni2(dhtp). To elucidate the mechanism of nanoparticle dispersion in condensed phases, we also studied the interactions among nanoparticles in various liquids, such as n-hexane, water and methanol. This work was performed at Pacific Northwest National Laboratory (PNNL) and was supported by the Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy (DOE). PNNL is operated by Battelle for the DOE. The authors also gratefully acknowledge support received from the National Energy Technology Laboratory of DOE's Office of Fossil Energy.

  1. Metal-organic and zeolite imidazolate frameworks (MOFs and ZIFs) for highly selective separations

    SciTech Connect (OSTI)

    Yaghi, Omar M

    2012-09-17

    Metal-organic and zeolite imidazolate frameworks (MOFs and ZIFs) have been investigated for the realization as separation media with high selectivity. These structures are held together with strong bonds, making them architecturally, chemically, and thermally stable. Therefore, employing well designed building units, it is possible to discover promising materials for gas and vapor separation. This grant was focused on the study of MOFs and ZIFs with these specific objectives: (i) to develop a strategy for producing MOFs and ZIFs that combine high surface areas with active sites for their use in gas adsorption and separation of small organic compounds, (ii) to introduce active sites in the framework by a post-synthetic modification and metalation of MOFs and ZIFs, and (iii) to design and synthesize MOFs with extremely high surface areas and large pore volumes to accommodate large amounts of guest molecules. By the systematic study, this effort demonstrated how to introduce active functional groups in the frameworks, and this is also the origin of a new strategy, which is termed isoreticular functionalization and metalation. However, a large pore volume is still a prerequisite feature. One of the solutions to overcome this challenge is an isoreticular expansion of a MOF's structure. With triangular organic linker and square building units, we demonstrated that MOF-399 has a unit cell volume 17 times larger than that of the first reported material isoreticular to it, and it has the highest porosity (94%) and lowest density (0.126 g cm-3) of any MOF reported to date. MOFs are not just low density materials; the guest-free form of MOF-210 demonstrates an ultrahigh porosity, whose BET surface area was estimated to be 6240 m2 g-1 by N2 adsorption measurements.

  2. Evaluating metal-organic frameworks for post-combustion carbon dioxide capture via temperature swing adsorption

    SciTech Connect (OSTI)

    Mason, JA; Sumida, K; Herm, ZR; Krishna, R; Long, JR

    2011-08-01

    Two representative metal-organic frameworks, Zn4O(BTB)(2)(BTB3- = 1,3,5-benzenetribenzoate; MOF-177) and Mg-2(dobdc) (dobdc(4-) = 1,4-dioxido-2,5-benzenedicarboxylate; Mg-MOF-74, CPO-27-Mg), are evaluated in detail for their potential use in post-combustion CO2 capture via temperature swing adsorption (TSA). Low-pressure single-component CO2 and N-2 adsorption isotherms were measured every 10 degrees C from 20 to 200 degrees C, allowing the performance of each material to be analyzed precisely. In order to gain a more complete understanding of the separation phenomena and the thermodynamics of CO2 adsorption, the isotherms were analyzed using a variety of methods. With regard to the isosteric heat of CO2 adsorption, Mg-2(dobdc) exhibits an abrupt drop at loadings approaching the saturation of the Mg2+ sites, which has significant implications for regeneration in different industrial applications. The CO2/N-2 selectivities were calculated using ideal adsorbed solution theory (IAST) for MOF-177, Mg-2(dobdc), and zeolite NaX, and working capacities were estimated using a simplified TSA model. Significantly, MOF-177 fails to exhibit a positive working capacity even at regeneration temperatures as high as 200 degrees C, while Mg-2(dobdc) reaches a working capacity of 17.6 wt% at this temperature. Breakthrough simulations were also performed for the three materials, demonstrating the superior performance of Mg-2(dobdc) over MOF-177 and zeolite NaX. These results show that the presence of strong CO2 adsorption sites is essential for a metal-organic framework to be of utility in post-combustion CO2 capture via a TSA process, and present a methodology for the evaluation of new metal-organic frameworks via analysis of single-component gas adsorption isotherms.

  3. Switching Kr/Xe Selectivity with Temperature in a Metal-Organic Framework

    SciTech Connect (OSTI)

    Fernandez, Carlos A.; Liu, Jian; Thallapally, Praveen K.; Strachan, Denis M.

    2012-05-16

    Krypton (Kr) and xenon (Xe) adsorption on two partially fluorinated metal-organic frameworks (FMOFCu and FMOFZn) with different cavity size and topologies were reported. FMOFCu shows an inversion in sorption selectivity toward Kr at temperatures below 0 C while FMOFZn does not. The 1D microtubes packed along the (101) direction connected through small bottleneck windows in FMOFCu appear to be the reason for this peculiar behavior. The FMOFCu shows an estimated Kr/Xe selectivity of 36 at 0.1 bar.

  4. A highly stable zeotype mesoporous zirconium metal-organic framework with ultralarge pores.

    SciTech Connect (OSTI)

    Feng, Dawei; Wang, Kecheng; Su, Jie; Liu, Tian-Fu; Park, Jihye; Wei, Zhangwen; Bosch, Mathieu; Yakovenko, Andrey; Zou, Xiaodong; Zhou, Hong-Cai

    2015-01-02

    Through topological rationalization, a zeotype mesoporous Zr-containing metal-organic framework (MOF), namely PCN-777, has been designed and synthesized. PCN-777 exhibits the largest cage size of 3.8nm and the highest pore volume of 2.8cm(3)g(-1) among reported Zr-MOFs. Moreover, PCN-777 shows excellent stability in aqueous environments, which makes it an ideal candidate as a support to incorporate different functional moieties. Through facile internal surface modification, the interaction between PCN-777 and different guests can be varied to realize efficient immobilization

  5. Metal-Organic Frameworks for Removal of Xe and Kr from Nuclear Fuel Reprocessing Plants

    SciTech Connect (OSTI)

    Liu, Jian; Thallapally, Praveen K.; Strachan, Denis M.

    2012-08-07

    Removal of Xenon (Xe) and Krypton (Kr) from in parts per million (ppm) levels were demonstrated for the first time using two well known metal-organic frameworks (MOFs), HKUST-1 and Ni/DOBDC. Results of an activated carbon were also included for comparison. Ni/DOBDC has higher Xe/Kr selectivities than those of the activated carbon. Moreover, results show that the Ni/DOBDC and HKUST-1 can selectively adsorb Xe and Kr from air even at 1000 ppm concentration. This shows a promising future for MOFs in a radioactive nuclides separation from spent fuel.

  6. Metal-Organic Frameworks for the Separation of O2 from Air - Energy

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Innovation Portal Industrial Technologies Industrial Technologies Find More Like This Return to Search Metal-Organic Frameworks for the Separation of O2 from Air Sandia National Laboratories Contact SNL About This Technology Publications: PDF Document Publication Market Sheet (340 KB) <br type="_moz" /> Mesoporous cages in MOF for O<sub>2</sub><br type="_moz" /> Mesoporous cages in MOF for O2 Technology Marketing Summary Pure molecular oxygen is

  7. Ab initio investigation on hydrogen adsorption capability in Zn and Cu-based metal organic frameworks

    SciTech Connect (OSTI)

    Tanuwijaya, V. V.; Hidayat, N. N. Agusta, M. K. Dipojono, H. K.

    2015-09-30

    One of the biggest challenge in material technology for hydrogen storage application is to increase hydrogen uptake in room temperature and pressure. As a class of highly porous material, Metal-Organic Frameworks (MOF) holds great potential with its tunable structure. However, little is known about the effect of metal cluster to its hydrogen storage capability. Investigation on this matter has been carried out carefully on small cluster of Zn and Cu-based MOF using first principles method. The calculation of two distinct building units of MOFs, namely octahedral and paddle-wheel models, have been done with B3LYP density functional method using 6-31G(d,p) and LANL2DZ basis sets. From geometry optimization of Zn-based MOF linked by benzene-dicarboxylate (MOF-5), it is found that hydrogen tends to keep distance from metal cluster group and stays above benzene ring. In the other hand, hydrogen molecule prefers to stay atop of the exposed Cu atom in Cu-based MOF system linked by the same linker group (Cu-bdc). Calculated hydrogen binding enthalpies for Zn and Cu octahedral cages at ZnO{sub 3} sites are 1.64kJ/mol and 2.73kJ/mol respectively, while hydrogen binding enthalpies for Zn and Cu paddle-wheel cages calculated on top of metal atoms are found to be at 6.05kJ/mol and 6.10kJ/mol respectively. Major difference between Zn-MOF-5 and Cu-bdc hydrogen uptake performance might be caused by unsaturated metal sites present in Cu-bdc system and the influence of their geometric structures, although a small difference on binding energy in the type of transition metal used is also observed. The comparison between Zn and Cu-based MOF may contribute to a comprehensive understanding of metal clusters and the importance of selecting best transition metal for design and synthesis of metal-organic frameworks.

  8. Computational screening of large molecule adsorption by metal-organic frameworks.

    SciTech Connect (OSTI)

    Allendorf, Mark D.; Greathouse, Jeffery A.

    2010-04-01

    Grand canonical Monte Carlo simulations were performed to investigate trends in low-pressure adsorption of a broad range of organic molecules by a set of metal-organic frameworks (MOFs). The organic analytes considered here are relevant to applications in chemical detection: small aromatics (o-, m-, and p-xylene), polycyclic aromatic hydrocarbons (naphthalene, anthracene, phenanthrene), explosives (TNT and RDX), and chemical warfare agents (GA and VM). The framework materials included several Zn-MOFs (IRMOFs 1-3, 7, 8), a Cr-MOF (CrMIL-53lp), and a Cu-MOF (HKUST-1). Many of the larger organics were significantly adsorbed by the target MOFs at low pressure, which is consistent with the exceptionally high isosteric heats of adsorption (25 kcal/mol - 60 kcal/mol) for this range of analyte. At a higher loading pressure of 101 kPa, the Zn-MOFs show a much higher volumetric uptake than either CrMIL-53-lp or HKUST-1 for all types of analyte. Within the Zn-MOF series, analyte loading is proportional to free volume, and loading decreases with increasing analyte size due to molecular packing effects. CrMIL-53lp showed the highest adsorption energy for all analytes, suggesting that this material may be suitable for low-level detection of organics.

  9. Ab initio carbon capture in open-site metal-organic frameworks

    SciTech Connect (OSTI)

    Dzubak, AL; Lin, LC; Kim, J; Swisher, JA; Poloni, R; Maximoff, SN; Smit, B; Gagliardi, L

    2012-08-19

    During the formation of metal-organic frameworks (MOFs), metal centres can coordinate with the intended organic linkers, but also with solvent molecules. In this case, subsequent activation by removal of the solvent molecules creates unsaturated 'open' metal sites known to have a strong affinity for CO2 molecules, but their interactions are still poorly understood. Common force fields typically underestimate by as much as two orders of magnitude the adsorption of CO2 in open-site Mg-MOF-74, which has emerged as a promising MOF for CO2 capture. Here we present a systematic procedure to generate force fields using high-level quantum chemical calculations. Monte Carlo simulations based on an ab initio force field generated for CO2 in Mg-MOF-74 shed some light on the interpretation of thermodynamic data from flue gas in this material. The force field describes accurately the chemistry of the open metal sites, and is transferable to other structures. This approach may serve in molecular simulations in general and in the study of fluid-solid interactions.

  10. Lithium inclusion in indium metal-organic frameworks showing increased surface area and hydrogen adsorption

    SciTech Connect (OSTI)

    Bosch, Mathieu; Zhang, Muwei; Feng, Dawei; Yuan, Shuai; Wang, Xuan; Chen, Ying-Pin; Zhou, Hong-Cai

    2014-12-01

    Investigation of counterion exchange in two anionic In-Metal-Organic Frameworks (In-MOFs) showed that partial replacement of disordered ammonium cations was achieved through the pre-synthetic addition of LiOH to the reaction mixture. This resulted in a surface area increase of over 1600% in (Li [In(1,3 − BDC){sub 2}]){sub n} and enhancement of the H{sub 2} uptake of approximately 275% at 80 000 Pa at 77 K. This method resulted in frameworks with permanent lithium content after repeated solvent exchange as confirmed by inductively coupled plasma mass spectrometry. Lithium counterion replacement appears to increase porosity after activation through replacement of bulkier, softer counterions and demonstrates tuning of pore size and properties in MOFs.

  11. Porphyrin-Metalation-Mediated Tuning of Photoredox Catalytic Properties in Metal–Organic Frameworks

    SciTech Connect (OSTI)

    Johnson, Jacob A.; Luo, Jian; Zhang, Xu; Chen, Yu-Sheng; Morton, Martha D.; Echeverría, Elena; Torres, Fernand E.; Zhang, Jian

    2015-09-04

    Photoredox catalytic activation of organic molecules via single-electron transfer processes has proven to be a mild and efficient synthetic methodology. However, the heavy reliance on expensive ruthenium and iridium complexes limits their applications for scale-up synthesis. To this end, photoactive metal–organic frameworks (MOFs) exhibit unique advantages as novel heterogeneous photocatalytic systems, yet their utilization toward organic transformations has been limited. Here we describe the preparation and synthetic applications of four isostructural porphyrinic MOFs, namely, UNLPF-10a, -10b, -11, and -12, which are composed of free base, InIII-, SnIVCl2-, and SnIV-porphyrin building blocks, respectively. We demonstrate that the metalation with high valent metal cations (InIII and SnIV) significantly modifies the electronic structure of porphyrin macrocycle and provides a highly oxidative photoexcited state that can undergo efficient reductive quenching processes to facilitate organic reactions. In particular, UNLPF-12 exhibits both outstanding photostability and efficient photocatalytic activities toward a range of important organic transformations including aerobic hydroxylation of arylboronic acids, amine coupling, and the Mannich reaction.

  12. Reusable Oxidation Catalysis Using Metal-Monocatecholato Species in a Robust Metal–Organic Framework

    SciTech Connect (OSTI)

    Fei, Honghan; Shin, JaeWook; Meng, Ying Shirley; Adelhardt, Mario; Sutter, Jörg; Meyer, Karsten; Cohen, Seth M.

    2014-04-02

    An isolated metal-monocatecholato moiety has been achieved in a highly robust metal–organic framework (MOF) by two fundamentally different postsynthetic strategies: postsynthetic deprotection (PSD) and postsynthetic exchange (PSE). Compared with PSD, PSE proved to be a more facile and efficient functionalization approach to access MOFs that could not be directly synthesized under solvothermal conditions. Metalation of the catechol functionality residing in the MOFs resulted in unprecedented Fe-monocatecholato and Cr-monocatecholato species, which were characterized by X-ray absorption spectroscopy, X-band electron paramagnetic resonance spectroscopy, and ⁵⁷Fe Mössbauer spectroscopy. The resulting materials are among the first examples of Zr(IV)-based UiO MOFs (UiO = University of Oslo) with coordinatively unsaturated active metal centers. Importantly, the Cr-metalated MOFs are active and efficient catalysts for the oxidation of alcohols to ketones using a wide range of substrates. Catalysis could be achieved with very low metal loadings (0.5–1 mol %). Unlike zeolite-supported, Cr-exchange oxidation catalysts, the MOF-based catalysts reported here are completely recyclable and reusable, which may make them attractive catalysts for ‘green’ chemistry processes.

  13. Formation mechanism of the secondary building unit in a chromium terephthalate metal-organic framework

    SciTech Connect (OSTI)

    Cantu Cantu, David; McGrail, B. Peter; Glezakou, Vassiliki Alexandra

    2014-09-18

    Based on density functional theory calculations and simulation, a detailed mechanism is presented on the formation of the secondary building unit (SBU) of MIL-101, a chromium terephthalate metal-organic framework (MOF). SBU formation is key to MOF nucleation, the rate-limiting step in the formation process of many MOFs. A series of reactions that lead to the formation of the SBU of MIL-101 is proposed in this work. Initial rate-limiting reactions form the metal cluster with three chromium (III) atoms linked to a central bridging oxygen. Terephthalate linkers play a key role as chromium (III) atoms are joined to linker carboxylate groups prior to the placement of the central bridging oxygen. Multiple linker addition reactions, which follow in different paths due to structural isomers, are limited by the removal of water molecules in the first chromium coordination shell. The least energy path is identified were all linkers on one face of the metal center plane are added first. A simple kinetic model based on transition state theory shows the rate of secondary building unit formation similar to the rate metal-organic framework nucleation. The authors are thankful to Dr. R. Rousseau for a critical reading of the manuscript. This research would not have been possible without the support of the Office of Fossil Energy, U.S. Department of Energy. This research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and the PNNL Institutional Computing (PIC) program located at Pacific Northwest National Laboratory.

  14. NMR relaxation and exchange in metal-organic frameworks for surface area screening

    SciTech Connect (OSTI)

    Chen, JJ; Mason, JA; Bloch, ED; Gygi, D; Long, JR; Reimer, JA

    2015-03-15

    We describe a robust screening technique that correlates the surface area of metal organic frameworks to the proton T-2 relaxation behavior of imbibed solvent at low field (13 MHz). In frameworks with small pore sizes (<1 nm) or strong solvent-framework interactions, diffusional exchange between the pore-confined and inter-particle solvent populations remains slow compared to the T-2 of the pore-confined solvent, allowing for a direct porosity analysis of the T-2 spectrum obtained from Laplace inversions. Increases in framework pore-size (>1 nm) lead to corresponding increases in the rate of solvent exchange, as confirmed by T-2 relaxation exchange (REXSY) experiments; increases in the pore size also increases the T-2 of the pore-confined solvent. The combination of these two effects results in comparable rates of relaxation and exchange, which precludes the direct analysis of Laplace inversions. Thus, two- and three-site kinetics models were applied to extract porosity from relaxation decays, thereby improving the utility of the porosity screening tool. (C) 2014 Elsevier Inc. All rights reserved.

  15. A scalable synthesis of a mesoporous metal-organic framework called NU-1000.

    SciTech Connect (OSTI)

    Wang, Timothy C.; Vermeulen, Nicolaas A.; Kim, In Soo; Martinson, Alex B. F.; Stoddart, J. Fraser; Hupp, Joseph T.; Farha, Omar K.

    2016-01-01

    The synthesis of NU-1000, a mesoporous metal-organic framework (MOF), can be conducted efficiently on a multigram scale from inexpensive starting materials. NU-1000 has been reported as an excellent candidate for gas separation and catalysis. In particular, it is ideal for the catalytic deactivation of nerve agents and shows great promise as a new generic platform for a wide range of applications. Multiple post-synthetic modification protocols have been developed using NU-1000 as the parent material, making it a potentially useful scaffold for several catalytic applications. The procedure for the preparation of NU-1000 can be scaled up reliably and is suitable for the production of 50 grams of the requisite organic linker and ?? grams of NU-1000. The entire synthesis is performed without purification by column chromatography and can be completed within 10 days.

  16. Separation of C2 Hydrocarbons by Porous Materials: Metal Organic Frameworks as Platform

    SciTech Connect (OSTI)

    Banerjee, Debasis; Liu, Jun; Thallapally, Praveen K.

    2014-12-22

    The effective separation of small hydrocarbon molecules (C1 C4) is an important process for petroleum industry, determining the end price of many essential commodities in our daily lives. Current technologies for separation of these molecules rely on energy intensive fractional distillation processes at cryogenic temperature, which is particularly difficult because of their similar volatility. In retrospect, adsorptive separation using solid state adsorbents might be a cost effective alternative. Several types of solid state adsorbents (e.g. zeolite molecular sieves) were tested for separation of small hydrocarbon molecules as a function of pressure, temperature or vacuum. Among different types of plausible adsorbents, metal organic frameworks (MOFs), a class of porous, crystalline, inorganic-organic hybrid materials, is particularly promising. In this brief comment article, we discuss the separation properties of different types of solid state adsorbents, with a particular emphasis on MOF based adsorbents for separation of C2 hydrocarbon molecules.

  17. Anion Binding in Metal-Organic Frameworks Functionalized with Urea Hydrogen-Bonding Groups

    SciTech Connect (OSTI)

    Custelcean, Radu; Moyer, Bruce A; Bryantsev, Vyacheslav S.; Hay, Benjamin P.

    2006-01-01

    A series of metal-organic frameworks (MOFs) functionalized with urea hydrogen-bonding groups has been synthesized and structurally analyzed by single-crystal X-ray diffraction to evaluate the efficacy of anion coordination by urea within the structural constraints of the MOFs. We found that urea-based functionalities may be used for anion binding within metal-organic frameworks when the tendency for urea{hor_ellipsis}urea self-association is decreased by strengthening the intramolecular CH{hor_ellipsis}O hydrogen bonding of N-phenyl substituents to the carbonyl oxygen atom. Theoretical calculations indicate that N,N'-bis(m-pyridyl)urea (BPU) and N,N'-bis(m-cyanophenyl)urea (BCPU) should have enhanced hydrogen-bonding donor abilities toward anions and decreased tendencies to self-associate into hydrogen-bonded tapes compared to other disubstituted ureas. Accordingly, BPU and BCPU were incorporated in MOFs as linkers through coordination of various Zn, Cu, and Ag transition metal salts, including Zn(ClO{sub 4}){sub 2}, ZnSO{sub 4}, Cu(NO{sub 3}){sub 2}, Cu(CF{sub 3}SO{sub 3}){sub 2}, AgNO{sub 3}, and AgSO{sub 3}CH{sub 3}. Structural analysis by single-crystal X-ray diffraction showed that these linkers are versatile anion binders, capable of chelate hydrogen bonding to all of the oxoanions explored. Anion coordination by the urea functionalities was found to successfully compete with urea self-association in all cases except for that of charge-diffuse perchlorate.

  18. Molecular mechanism of hydrocarbons binding to the metalorganic framework

    SciTech Connect (OSTI)

    Sun, Xiuquan; Wick, Collin D.; Thallapally, Praveen K.; McGrail, B. Peter; Dang, Liem X.

    2011-01-07

    The adsorption and diffusivity of methane, ethane, n-butane, n-hexane and cyclohexane in a metal organic framework (MOF) with the organic linker tetrakis[4-(carboxyphenyl)oxamethyl]methane, the metal salt, Zn2+, and organic pillar, 4,4-bipyridin was studied using molecular dynamics simulations. For the n-alkanes, the longer the chain, the lower the free energy of adsorption, which was attributed to a greater number of contacts between the alkane and MOF. Cyclohexane had a slightly higher adsorption free energy than n-hexane. Furthermore, for cyclo- and n-hexane, there were no significant differences in adsorption free energies between systems with low to moderate loadings. The diffusivity of the n-alkanes was found to strongly depend on chain length with slower diffusion for longer chains. Cyclohexane had no effective diffusion, suggesting that the selectivity the MOF has towards n-hexane over cyclohexane is the result of kinetics instead of energetics. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for DOE.

  19. System and method for generating and/or screening potential metal-organic frameworks

    SciTech Connect (OSTI)

    Wilmer, Christopher E; Leaf, Michael; Snurr, Randall Q; Farha, Omar K; Hupp, Joseph T

    2015-04-21

    A system and method for systematically generating potential metal-organic framework (MOFs) structures given an input library of building blocks is provided herein. One or more material properties of the potential MOFs are evaluated using computational simulations. A range of material properties (surface area, pore volume, pore size distribution, powder x-ray diffraction pattern, methane adsorption capability, and the like) can be estimated, and in doing so, illuminate unidentified structure-property relationships that may only have been recognized by taking a global view of MOF structures. In addition to identifying structure-property relationships, this systematic approach to identify the MOFs of interest is used to identify one or more MOFs that may be useful for high pressure methane storage.

  20. System and method for generating and/or screening potential metal-organic frameworks

    SciTech Connect (OSTI)

    Wilmer, Christopher E; Leaf, Michael; Snurr, Randall Q; Farha, Omar K; Hupp, Joseph T

    2014-12-02

    A system and method for systematically generating potential metal-organic framework (MOFs) structures given an input library of building blocks is provided herein. One or more material properties of the potential MOFs are evaluated using computational simulations. A range of material properties (surface area, pore volume, pore size distribution, powder x-ray diffraction pattern, methane adsorption capability, and the like) can be estimated, and in doing so, illuminate unidentified structure-property relationships that may only have been recognized by taking a global view of MOF structures. In addition to identifying structure-property relationships, this systematic approach to identify the MOFs of interest is used to identify one or more MOFs that may be useful for high pressure methane storage.

  1. Adsorption and diffusion of carbon dioxide on metal-organic framework (MOF-5)

    SciTech Connect (OSTI)

    Zhao, Z.X.; Li, Z.; Lin, Y.S.

    2009-11-15

    Adsorption equilibrium and diffusion of CO{sub 2} on microporous metal-organic frameworks (MOF-5, or IRMOF-1) crystals were experimentally studied by the gravimetric method in the pressure range up to 1 atm. The MOF-5 crystal cubes of about 40-60 {mu} m in sizes were synthesized by the solvothermal method. Freundlich adsorption isotherm equation can fit well CO{sub 2} adsorption isotherms on MOF-5, with isosteric heat of adsorption of about 34 kJ/mol. Diffusion coefficient of CO{sub 2} in the MOF-5 is in the range of 8.1-11.5 x 10{sup -9} cm{sup 2}/s in 295-331K with activation energy of 7.61 kJ/mol. MOF-5 offers attractive adsorption properties as an adsorbent for separation of CO{sub 2} from flue gas.

  2. Metal-Organic Framework Thin Films as Stationary Phases in Microfabricated Gas-Chromatography Columns.

    SciTech Connect (OSTI)

    Read, Douglas; Sillerud, Colin Halliday

    2016-01-01

    The overarching goal of this project is to integrate Sandia's microfabricated gas-chromatography ( GC) columns with a stationary phase material that is capable of retaining high-volatility chemicals and permanent gases. The successful integration of such a material with GCs would dramatically expand the repertoire of detectable compounds for Sandia's various microanalysis systems. One such promising class of candidate materials is metal-organic frameworks (MOFs). In this report we detail our methods for controlled deposition of HKUST-1 MOF stationary phases within GC columns. We demonstrate: the chromatographic separation of natural gas; a method for determining MOF film thickness from chromatography alone; and the first-reported GC x GC separation of natural gas -- in general -- let alone for two disparate MOF stationary phases. In addition we determine the fundamental thermodynamic constant for mass sorption, the partition coefficient, for HKUST-1 and several light hydrocarbons and select toxic industrial chemicals.

  3. Unraveling the multi-functional behavior in a series of Metal Organic Frameworks

    SciTech Connect (OSTI)

    Sanda, Suresh; Biswas, Soumava; Parshamoni, Srinivasulu; Konar, Sanjit

    2015-09-15

    Three new 2D/3D Metal-Organic Frameworks (MOFs), ([Zn(2,6-ndc)(aldrithiol)]·3(H{sub 2}O)){sub n} (1), ([Co(2,6-ndc)(aldrithiol)(H{sub 2}O){sub 2}]·2(H{sub 2}O)){sub n} (2), ([Cd{sub 2}(2,6-ndc){sub 2}(aldrithiol){sub 2}(H{sub 2}O){sub 2}]·(aldrithiol)·(EtOH)·3(H{sub 2}O)){sub n} (3), (2,6-ndc = 2,6-naphthalene dicarboxylic acid; aldrithiol = 4,4'-dipyridyl disulphide) have been synthesized and structurally characterized. Compounds 1 and 2 have 2D layered architectures with similar framework topology whereas 3 is a 2-fold interwoven three dimensional framework. Sorption studies reveal that compounds 1-3 selectively adsorbs CO{sub 2} over other gases and H{sub 2}O over other solvents. Proton conductivity study of compounds 1 and 2 show highest values of 6.73 x 10{sup -7} S.cm{sup -1}, 1.96 x 10{sup -5} S.cm{sup -1} at 318 K and 95% RH and these values are humidity dependent. Photoluminescent properties of compounds 1 and 3 show metal perturbed (π*–π and π*-n) intra ligand charge transfer transitions. Additionally, Compound 3 also displays reversible adsorption of molecular iodine. - Graphical abstarct: Three new 2D/3D interpenetrated MOFs are synthesized and their multifunctional material properties such as adsorption, proton conduction, iodine adsorption as well as luminscence have been explored. - Highlights: • We report multifunctional material properties in a series MOFs (Compounds 1-3) • All the compounds show selective adsorption of CO{sub 2} over other gases and H{sub 2}O over other solvents. • The proton conduction property studies of all the compounds reveal the humidity dependent conductivity. • Compound 2 shows reversible adsorption of molecular iodine in the framework. • Photoluminescent properties of compounds 1 and 2 show metal perturbed intra ligand charge transfer transitions.

  4. Metal-Organic Frameworks as Adsorbents for Hydrogen Purification and Precombustion Carbon Dioxide Capture

    SciTech Connect (OSTI)

    Herm, Zoey R; Swisher, Joe A; Smit, Berend; Krishna, Rajamani; Long, Jeffrey R

    2011-04-20

    Selected metal–organic frameworks exhibiting representative properties—high surface area, structural flexibility, or the presence of open metal cation sites—were tested for utility in the separation of CO₂ from H₂ via pressure swing adsorption. Single-component CO₂ and H₂ adsorption isotherms were measured at 313 K and pressures up to 40 bar for Zn₄O(BTB)₂ (MOF-177, BTB3- = 1,3,5-benzenetribenzoate), Be12(OH)12(BTB)₄ (Be-BTB), Co(BDP) (BDP2- = 1,4-benzenedipyrazolate), H₃[(Cu₄Cl)₃(BTTri)₈] (Cu-BTTri, BTTri3- = 1,3,5-benzenetristriazolate), and Mg₂(dobdc) (dobdc4- = 1,4-dioxido-2,5-benzenedicarboxylate). Ideal adsorbed solution theory was used to estimate realistic isotherms for the 80:20 and 60:40 H₂/CO₂ gas mixtures relevant to H₂ purification and precombustion CO₂ capture, respectively. In the former case, the results afford CO₂/H₂ selectivities between 2 and 860 and mixed-gas working capacities, assuming a 1 bar purge pressure, as high as 8.6 mol/kg and 7.4 mol/L. In particular, metal–organic frameworks with a high concentration of exposed metal cation sites, Mg₂(dobdc) and Cu-BTTri, offer significant improvements over commonly used adsorbents, indicating the promise of such materials for applications in CO₂}/H₂ separations.

  5. Collaborative Triple Framework Interpenetration and Immobilization of Open Metal Sites within a Microporous Mixed Metal-Organic Framework for Highly Selective Gas Adsorption

    SciTech Connect (OSTI)

    Zhang, Zhangjing; Xiang, Sheng-Chang; Hong, Kunlun; Das, Madhab; Arman, Hadi; Garcia, Maya; Mondal, Jalal; Chen, Banglin

    2012-01-01

    A three-dimensional triply interpenetrated mixed metal-organic framework, Zn{sub 2}(BBA){sub 2}(CuPyen) {center_dot} G{sub x} (M'MOF-20; BBA = biphenyl-4,4'-dicarboxylate; G = guest solvent molecules), of primitive cubic net was obtained through the solvothermal reaction of Zn(NO{sub 3}){sub 2}, biphenyl-4,4'-dicarboxylic acid, and the salen precursor Cu(PyenH{sub 2})(NO{sub 3}){sub 2} by a metallo-ligand approach. The triple framework interpenetration has stabilized the framework in which the activated M'MOF-20a displays type-I N{sub 2} gas sorption behavior with a Langmuir surface area of 62 m{sup 2} g{sup -1}. The narrow pores of about 3.9 {angstrom} and the open metal sites on the pore surfaces within M'MOF-20a collaboratively induce its highly selective C{sub 2}H{sub 2}/CH{sub 4} and CO{sub 2}/CH{sub 4} gas separation at ambient temperature.

  6. High-Throughput Methodology for Discovery of Metal-Organic Frameworks...

    Broader source: Energy.gov (indexed) [DOE]

    High Throughput Combinatorial Screening of Biometic Metal-Organic Materials for Military Hydrogen-Storage Materials (New Joint Miami UNREL DoDDLA Project) (presentation) High ...

  7. Metal-Organic Frameworks: Literature Survey and Recommendation of Potential Sorbent Materials

    SciTech Connect (OSTI)

    Baumann, T F

    2010-04-29

    Metal-organic frameworks (MOFs) are a special type of porous material with a number of unique properties, including exceptionally high surface areas, large internal pore volumes (void space) and tunable pore sizes. These materials are prepared through the assembly of molecular building blocks into ordered three-dimensional structures. The bulk properties of the MOF are determined by the nature of the building blocks and, as such, these materials can be designed with special characteristics that cannot be realized in other sorbent materials, like activated carbons. For example, MOFs can be constructed with binding sites or pockets that can exhibit selectivity for specific analytes. Alternatively, the framework can be engineered to undergo reversible dimensional changes (or 'breathing') upon interaction with an analyte, effectively trapping the molecule of interest in the lattice structure. In this report, we have surveyed the 4000 different MOF structures reported in the open literature and provided recommendations for specific MOF materials that should be investigated as sorbents for this project.

  8. Sulfation of metal-organic framework: Opportunities for acid catalysis and proton conductivity

    SciTech Connect (OSTI)

    Goesten, M.G.; Stavitski, E.; Juan-Alcaniz, J.; Ramos-Fernandez, E.V.; Sai Sankar Gupta, K.B.; van Bekkum, H.; Gascon, J. and Kapteijn, F.

    2011-05-24

    A new post-functionalization method for metal-organic frameworks (MOFs) has been developed to introduce acidity for catalysis. Upon treatment with a mixture of triflic anhydride and sulfuric acid, chemically stable MOF structures MIL-101(Cr) and MIL-53(Al) can be sulfated, resulting in a Broensted sulfoxy acid group attached to up to 50% of the aromatic terephthalate linkers of the structure. The sulfated samples have been extensively characterized by solid-state NMR, XANES, and FTIR spectroscopy. The functionalized acidic frameworks show catalytic activity similar to that of acidic polymers like Nafion{reg_sign} display in the esterification of n-butanol with acetic acid (TOF {approx} 1 min{sup -1} {at} 343 K). Water adsorbs strongly up to 4 molecules per sulfoxy acid group, and an additional 2 molecules are taken up at lower temperatures in the 1-D pore channels of S-MIL-53(Al). The high water content and Broensted acidity provide the structure S-MIL-53(Al) a high proton conductivity up to moderate temperatures.

  9. Interpenetrating metal-organic frameworks formed by self-assembly of tetrahedral and octahedral building blocks

    SciTech Connect (OSTI)

    Lu Yongming; Lan Yaqian; Xu Yanhong; Su Zhongmin; Li Shunli; Zang Hongying; Xu Guangjuan

    2009-11-15

    To investigate the relationship between topological types and molecular building blocks (MBBs), we have designed and synthesized a series of three-dimensional (3D) interpenetrating metal-organic frameworks based on different polygons or polyhedra under hydrothermal conditions, namely [Cd(bpib){sub 0.5}(L{sup 1})] (1), [Cd(bpib){sub 0.5}(L{sup 2})].H{sub 2}O (2), [Cd(bpib){sub 0.5}(L{sup 3})] (3) and [Cd(bib){sub 0.5}(L{sup 1})] (4), where bpib=1,4-bis(2-(pyridin-2-yl)-1H-imidazol-1-yl)butane, bib=1,4-bis(1H-imidazol-1-yl)butane, H{sub 2}L{sup 1}=4-(4-carboxybenzyloxy)benzoic acid, H{sub 2}L{sup 2}=4,4'-(ethane-1,2-diylbis(oxy))dibenzoic acid and H{sub 2}L{sup 3}=4,4'-(1,4-phenylenebis(methylene))bis(oxy)dibenzoic acid, respectively. Their structures have been determined by single crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric (TG) analyses. Compounds 1-3 display alpha-Po topological nets with different degrees of interpenetration based on the similar octahedral [Cd{sub 2}(-COO){sub 4}] building blocks. Compound 4 is a six-fold interpenetrating diamondoid net based on tetrahedral MBBs. By careful inspection of these structures, we find that various carboxylic ligands and N-donor ligands with different coordination modes and conformations, and metal centers with different geometries are important for the formation of the different MBBs. It is believed that different topological types lie on different MBBs with various polygons or polyhedra. Such as four- and six-connected topologies are formed by tetrahedral and octahedral building blocks. In addition, with the increase of carboxylic ligands' length, the degrees of interpenetration have been changed in the alpha-Po topological nets. And the luminescent properties of these compounds have been investigated in detail. - Graphical abstract: A series of three-dimensional interpenetrating metal-organic frameworks based on different polygons or polyhedra

  10. Anion Coordination in Metal-Organic Frameworks Functionalized with Urea Hydrogen-Bonding Groups

    SciTech Connect (OSTI)

    Custelcean, Radu; Moyer, Bruce A.; Bryantsev, Vyacheslav; Hay, Benjamin P.

    2005-12-15

    A series of metal-organic frameworks (MOFs) functionalized with urea hydrogen-bonding groups have been designed, synthesized, and structurally analyzed by single crystal X-ray diffraction to evaluate the efficacy of anion binding within the structural constraints of the MOFs. We found that urea-based functionalities may be used for anion binding within metal-organic frameworks when the tendency for urea???urea self-association is decreased by strengthening the intramolelcular CH???O hydrogen bonding of N-phenyl substituents to the carbonyl oxygen atom. Theoretical calculations indicate that N,N?-bis(m-pyridyl)urea (BPU) and N,N?-bis(m-cyanophenyl)urea (BCPU) should have enhanced hydrogen-bonding donor abilities toward anions and decreased tendencies to self-associate into hydrogen-bonded chains compared to other disubstituted ureas. Accordingly, BPU and BCPU were incorporated in MOFs as linkers through coordination of various Zn, Cu, and Ag transition metal salts, including Zn(ClO4)2, ZnSO4, Cu(NO3)2, Cu(CF3SO3)2, AgNO3 and AgSO3CH3. Structural analysis by single-crystal X-ray diffraction showed that these linkers are versatile anion binders, capable of chelate hydrogen bonding to all of the oxoanions explored. Anion binding by the urea functionalities was found to successfully compete with urea self-association in all cases except for that of charge-diffuse perchlorate. This research was sponsored by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the U.S. Department of Energy, under contract number DE-AC05-00OR22725 with Oak Ridge National Laboratory (managed by UT-Battelle, LLC), and performed at Oak Ridge National laboratory and Pacific Northwest National Laboratory (managed by Battelle for the U.S. Department of Energy under contract DE-AC05-76RL01830). This research was performed in part using the Molecular Science Computing Facility (MSCF) in the William R. Wiley Environmental Molecular Sciences laboratory

  11. Water Adsorption in Porous Metal-Organic Frameworks and Related Materials

    SciTech Connect (OSTI)

    Furukawa, H; Gandara, F; Zhang, YB; Jiang, JC; Queen, WL; Hudson, MR; Yaghi, OM

    2014-03-19

    Water adsorption in porous materials is important for many applications such as dehumidification, thermal batteries, and delivery of drinking water in remote areas. In this study, we have identified three criteria for achieving high performing porous materials for water adsorption. These criteria deal with condensation pressure of water in the pores, uptake capacity, and recyclability and water stability of the material. In search of an excellently performing porous material, we have studied and compared the water adsorption properties of 23 materials, 20 of which are metal organic frameworks (MOFs). Among the MOFs are 10 zirconium(IV) MOFs with a subset of these, MOF-801-SC (single crystal form), -802, -805, -806, -808, -812, and -841 reported for the first time. MOF-801-P (microcrystalline powder form) was reported earlier and studied here for its water adsorption properties. MOF-812 was only made and structurally characterized but not examined for water adsorption because it is a byproduct of MOF-841 synthesis. All the new zirconium MOFs are made from the Zr6O4(OH)(4)(-CO2)(n) secondary building units (n = 6, 8, 10, or 12) and variously shaped carboxyl organic linkers to make extended porous frameworks. The permanent porosity of all 23 materials was confirmed and their water adsorption measured to reveal that MOF-801-P and MOF-841 are the highest performers based on the three criteria stated above; they are water stable, do not lose capacity after five adsorption/desorption cycles, and are easily regenerated at room temperature. An X-ray single-crystal study and a powder neutron diffraction study reveal the position of the water adsorption sites in MOF-801 and highlight the importance of the intermolecular interaction between adsorbed water molecules within the pores.

  12. Design and Synthesis of Novel Porous Metal-Organic Frameworks (MOFs) Toward High Hydrogen Storage Capacity

    SciTech Connect (OSTI)

    Mohamed, Eddaoudi; Zaworotko, Michael; Space, Brian; Eckert, Juergen

    2013-05-08

    Statement of Objectives: 1. Synthesize viable porous MOFs for high H2 storage at ambient conditions to be assessed by measuring H2 uptake. 2. Develop a better understanding of the operative interactions of the sorbed H2 with the organic and inorganic constituents of the sorbent MOF by means of inelastic neutron scattering (INS, to characterize the H2-MOF interactions) and computational studies (to interpret the data and predict novel materials suitable for high H2 uptake at moderate temperatures and relatively low pressures). 3. Synergistically combine the outcomes of objectives 1 and 2 to construct a made-to-order inexpensive MOF that is suitable for super H2 storage and meets the DOE targets - 6% H2 per weight (2kWh/kg) by 2010 and 9% H2 per weight (3kWh/kg) by 2015. The ongoing research is a collaborative experimental and computational effort focused on assessing H2 storage and interactions with pre-selected metal-organic frameworks (MOFs) and zeolite-like MOFs (ZMOFs), with the eventual goal of synthesizing made-to-order high H2 storage materials to achieve the DOE targets for mobile applications. We proposed in this funded research to increase the amount of H2 uptake, as well as tune the interactions (i.e. isosteric heats of adsorption), by targeting readily tunable MOFs:

  13. Creating a Discovery Platform for Confined-Space Chemistry and Materials: Metal-Organic Frameworks.

    SciTech Connect (OSTI)

    Allendorf, Mark D.; Greathouse, Jeffery A.; Simmons, Blake

    2008-09-01

    Metal organic frameworks (MOF) are a recently discovered class of nanoporous, defect-free crystalline materials that enable rational design and exploration of porous materials at the molecular level. MOFs have tunable monolithic pore sizes and cavity environments due to their crystalline nature, yielding properties exceeding those of most other porous materials. These include: the lowest known density (91% free space); highest surface area; tunable photoluminescence; selective molecular adsorption; and methane sorption rivaling gas cylinders. These properties are achieved by coupling inorganic metal complexes such as ZnO4 with tunable organic ligands that serve as struts, allowing facile manipulation of pore size and surface area through reactant selection. MOFs thus provide a discovery platform for generating both new understanding of chemistry in confined spaces and novel sensors and devices based on their unique properties. At the outset of this project in FY06, virtually nothing was known about how to couple MOFs to substrates and the science of MOF properties and how to tune them was in its infancy. An integrated approach was needed to establish the required knowledge base for nanoscale design and develop methodologies integrate MOFs with other materials. This report summarizes the key accomplishments of this project, which include creation of a new class of radiation detection materials based on MOFs, luminescent MOFs for chemical detection, use of MOFs as templates to create nanoparticles of hydrogen storage materials, MOF coatings for stress-based chemical detection using microcantilevers, and %22flexible%22 force fields that account for structural changes in MOFs that occur upon molecular adsorption/desorption. Eight journal articles, twenty presentations at scientific conferences, and two patent applications resulted from the work. The project created a basis for continuing development of MOFs for many Sandia applications and succeeded in securing %242

  14. Facile xenon capture and release at room temperature using a metal-organic framework: a comparison with activated charcoal

    SciTech Connect (OSTI)

    Thallapally, Praveen K.; Grate, Jay W.; Motkuri, Radha K.

    2012-01-11

    Two well known Metal organic frameworks (MOF-5, NiDOBDC) were synthesized and studied for facile xenon capture and separation. Our results indicate the NiDOBDC adsorbs significantly more xenon than MOF-5, releases it more readily than activated carbon, and is more selective for Xe over Kr than activated carbon.

  15. Formation of a new archetypal Metal-Organic Framework from a simple monatomic liquid

    SciTech Connect (OSTI)

    Metere, Alfredo Oleynikov, Peter; Dzugutov, Mikhail; O’Keeffe, Michael

    2014-12-21

    We report a molecular-dynamics simulation of a single-component system of particles interacting via a spherically symmetric potential that is found to form, upon cooling from a liquid state, a low-density porous crystalline phase. Its structure analysis demonstrates that the crystal can be described by a net with a topology that belongs to the class of topologies characteristic of the Metal-Organic Frameworks (MOFs). The observed net is new, and it is now included in the Reticular Chemistry Structure Resource database. The observation that a net topology characteristic of MOF crystals, which are known to be formed by a coordination-driven self-assembly process, can be reproduced by a thermodynamically stable configuration of a simple single-component system of particles opens a possibility of using these models in studies of MOF nets. It also indicates that structures with MOF topology, as well as other low-density porous crystalline structures can possibly be produced in colloidal systems of spherical particles, with an appropriate tuning of interparticle interaction.

  16. Nanomechanical investigation of thin-film electroceramic/metal-organic framework multilayers

    SciTech Connect (OSTI)

    Best, James P. E-mail: engelbert.redel@kit.edu Michler, Johann; Maeder, Xavier; Liu, Jianxi; Wang, Zhengbang; Tsotsalas, Manuel; Liu, Jinxuan; Gliemann, Hartmut; Weidler, Peter G.; Redel, Engelbert E-mail: engelbert.redel@kit.edu Wöll, Christof E-mail: engelbert.redel@kit.edu; Röse, Silvana; Oberst, Vanessa; Walheim, Stefan

    2015-09-07

    Thin-film multilayer stacks of mechanically hard magnetron sputtered indium tin oxide (ITO) and mechanically soft highly porous surface anchored metal-organic framework (SURMOF) HKUST-1 were studied using nanoindentation. Crystalline, continuous, and monolithic surface anchored MOF thin films were fabricated using a liquid-phase epitaxial growth method. Control over respective fabrication processes allowed for tuning of the thickness of the thin film systems with a high degree of precision. It was found that the mechanical indentation of such thin films is significantly affected by the substrate properties; however, elastic parameters were able to be decoupled for constituent thin-film materials (E{sub ITO} ≈ 96.7 GPa, E{sub HKUST−1} ≈ 22.0 GPa). For indentation of multilayer stacks, it was found that as the layer thicknesses were increased, while holding the relative thickness of ITO and HKUST-1 constant, the resistance to deformation was significantly altered. Such an observation is likely due to small, albeit significant, changes in film texture, interfacial roughness, size effects, and controlling deformation mechanism as a result of increasing material deposition during processing. Such effects may have consequences regarding the rational mechanical design and utilization of MOF-based hybrid thin-film devices.

  17. Lewis Acid–Base Interactions between Polysulfides and Metal Organic Framework in Lithium Sulfur Batteries

    SciTech Connect (OSTI)

    Zheng, Jianming; Tian, Jian; Wu, Dangxin; Gu, Meng; Xu, Wu; Wang, Chongmin; Gao, Fei; Engelhard, Mark H.; Zhang, Ji-Guang; Liu, Jun; Xiao, Jie

    2014-05-14

    Lithium–sulfur (Li–S) battery is one of the most promising energy storage systems because of its high specific capacity of 1675 mAh g–1 based on sulfur. However, the rapid capacity degradation, mainly caused by polysulfide dissolution, remains a significant challenge prior to practical applications. This work demonstrates that a novel Ni-based metal organic framework (Ni-MOF), Ni6(BTB)4(BP)3 (BTB = benzene-1,3,5-tribenzoate and BP = 4,4'-bipyridyl), can remarkably immobilize polysulfides within the cathode structure through physical and chemical interactions at molecular level. The capacity retention achieves up to 89% after 100 cycles at 0.1 C. Finally, the excellent performance is attributed to the synergistic effects of the interwoven mesopores (~2.8 nm) and micropores (~1.4 nm) of Ni-MOF, which first provide an ideal matrix to confine polysulfides, and the strong interactions between Lewis acidic Ni(II) center and the polysulfide base, which significantly slow down the migration of soluble polysulfides out of the pores, leading to the excellent cycling performance of Ni-MOF/S composite.

  18. Carborane-Based Metal-Organic Framework with High Methane and Hydrogen Storage Capacities

    SciTech Connect (OSTI)

    Kennedy, RD; Krungleviciute, V; Clingerman, DJ; Mondloch, JE; Peng, Y; Wilmer, CE; Sarjeant, AA; Snurr, RQ; Hupp, JT; Yildirim, T; Farha, OK; Mirkin, CA

    2013-09-10

    A Cu-carborane-based metal organic framework (MOF), NU-135, which contains a quasi-spherical para-carborane moiety, has been synthesized and characterized. NU-135 exhibits a pore volume of 1.02 cm(3)/g and a gravimetric BET surface area of ca. 2600 m(2)/g, and thus represents the first highly porous carborane-based MOF. As a consequence of the, unique geometry of the carborane unit, NU-135 has a very high volumetric BET surface area of ca. 1900 m(2)/cm(3). CH4, CO2, and H-2 adsorption isotherms were measured over a broad range of pressures and temperatures and are in good agreement with computational predictions. The methane storage capacity of NU-135 at 35 bar and 298 K is ca. 187 v(STP)/v. At 298 K, the pressure required to achieve a methane storage density comparable to that of a compressed natural gas (CNG) tank pressurized to 212 bar, which is a typical storage pressure, is only 65 bar. The methane working capacity (5-65 bar) is 170 v(STP)/v. The volumetric hydrogen storage capacity at 55 bar and 77 K is 49 g/L. These properties are comparable to those of current record holders in the area of methane and hydrogen storage. This initial example lays the groundwork for carborane-based materials with high surface areas.

  19. A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Hod, Idan; Deria, Pravas; Bury, Wojciech; Mondloch, Joseph E.; Kung, Chung-Wei; So, Monica; Sampson, Matthew D.; Peters, Aaron W.; Kubiak, Cliff P.; Farha, Omar K.; et al

    2015-09-14

    The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200 mV at a benchmark current density of 10 mA cm−2. In conclusion, althoughmore » the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst.« less

  20. A Combined Experimental and Computational Study on the Stability of Nanofluids Containing Metal Organic Frameworks

    SciTech Connect (OSTI)

    Annapureddy, Harsha Vardhan Reddy; Nune, Satish K.; Motkuri, Radha K.; McGrail, B. Peter; Dang, Liem X.

    2015-01-23

    Computational studies on nanofluids composed of metal organic frameworks (MOFs) were performed using molecular modeling techniques. Grand Canonical Monte Carlo (GCMC) simulations were used to study adsorption behavior of 1,1,1,3,3-pentafluoropropane (R-245fa) in a MIL-101 MOF at various temperatures. To understand the stability of the nanofluid composed of MIL-101 particles, we performed molecular dynamics simulations to compute potentials of mean force between hypothetical MIL-101 fragments terminated with two different kinds of modulators in R-245fa and water. Our computed potentials of mean force results indicate that the MOF particles tend to disperse better in water than in R-245fa. The reasons for this observation were analyzed and discussed. Our results agree with experimental results indicating that the employed potential models and modeling approaches provide good description of molecular interactions and the reliabilities. Work performed by LXD was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Work performed by HVRA, SKN, RKM, and PBM was supported by the Office of Energy Efficiency and Renewable Energy, Geothermal Technologies Program. Pacific Northwest National Laboratory is a multiprogram national laboratory operated for DOE by Battelle.

  1. A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution

    SciTech Connect (OSTI)

    Hod, Idan; Deria, Pravas; Bury, Wojciech; Mondloch, Joseph E.; Kung, Chung-Wei; So, Monica; Sampson, Matthew D.; Peters, Aaron W.; Kubiak, Cliff P.; Farha, Omar K.; Hupp, Joseph T.

    2015-09-14

    The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200 mV at a benchmark current density of 10 mA cm−2. In conclusion, although the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst.

  2. Diffusion of methane and other alkanes in metal-organic frameworks for natural gas storage

    SciTech Connect (OSTI)

    Borah, B; Zhang, HD; Snurr, RQ

    2015-03-03

    Diffusion of methane, ethane, propane and n-butane was studied within the micropores of several metal organic frameworks (MOFs) of varying topologies, including the MOFs PCN-14, NU-125, NU-1100 and DUT-49. Diffusion coefficients of the pure components, as well as methane/ethane, methane/ propane and methane/butane binary mixtures, were calculated using molecular dynamics simulations to understand the effect of the longer alkanes on uptake of natural gas in MOB. The calculated self diffusion coefficients of all four components are on the order of 10(-8) m(2)/s. The diffusion coefficients of the pure components decrease as a function of chain length in all of the MOFs studied and show different behaviour as a function of loading in different MOB. The self-diffusivities follow the trend DPCN-14 < DNU-125 approximate to DNU-1100 < DDUT-49, which is exactly the reverse order of the densities of the MOFs: PCN-14 > NU-125 approximate to NU-1100 > DUT-49. By comparing the diffusion of pure methane and methane mixtures vvith the higher alkancs, it is observed that the diffusivity of methane is unaffected by the presence of the higher alkanes in the MOFs considered, indicating that the diffusion path of methane is not blocked by the higher alkanes present in natural gas. (C) 2014 Elsevier Ltd. All rights reserved.

  3. Syntheses, structures and tunable luminescence of lanthanide metal-organic frameworks based on azole-containing carboxylic acid ligand

    SciTech Connect (OSTI)

    Zhao, Dian; Rao, Xingtang; Yu, Jiancan; Cui, Yuanjing Yang, Yu; Qian, Guodong

    2015-10-15

    Design and synthesis of a series of isostructural lanthanide metal-organic frameworks (LnMOFs) serving as phosphors by coordinate the H{sub 2}TIPA (5-(1H-tetrazol-5-yl)isophthalic acid) ligands and lanthanide ions is reported. The color of the luminescence can be tuned by adjusting the relative concentration of the lanthanide ions in the host framework GdTIPA, and near-pure-white light emission can be achieved. - Graphical abstract: Lanthanide metal-organic frameworks (LnMOFs) with tunable luminescence were synthesized using an azole-containing carboxylic acid as ligand. - Highlights: • A series of isostructural LnMOFs serving as phosphor is reported. • We model the GdTIPA: Tb{sup 3+}, Eu{sup 3+} which can tune color and emit white light. • The scheme and mechanism of luminescent LnMOFs are also presented and discussed.

  4. Composite Membranes for CO2 Capture: High Performance Metal Organic Frameworks/Polymer Composite Membranes for Carbon Dioxide Capture

    SciTech Connect (OSTI)

    2010-07-01

    IMPACCT Project: A team of six faculty members at Georgia Tech are developing an enhanced membrane by fitting metal organic frameworks, compounds that show great promise for improved carbon capture, into hollow fiber membranes. This new material would be highly efficient at removing CO2 from the flue gas produced at coal-fired power plants. The team is analyzing thousands of metal organic frameworks to identify those that are most suitable for carbon capture based both on their ability to allow coal exhaust to pass easily through them and their ability to select CO2 from that exhaust for capture and storage. The most suitable frameworks would be inserted into the walls of the hollow fiber membranes, making the technology readily scalable due to their high surface area. This composite membrane would be highly stable, withstanding the harsh gas environment found in coal exhaust.

  5. Stress-induced chemical detection using flexible metal-organic frameworks.

    SciTech Connect (OSTI)

    Allendorf, Mark D.; Hesketh, Peter J.; Gall, Kenneth A.; Choudhury, A.; Pikarsky, J.; Andruszkiewicz, Leanne; Houk, Ronald J. T.; Talin, Albert Alec

    2009-09-01

    In this work we demonstrate the concept of stress-induced chemical detection using metal-organic frameworks (MOFs) by integrating a thin film of the MOF HKUST-1 with a microcantilever surface. The results show that the energy of molecular adsorption, which causes slight distortions in the MOF crystal structure, can be efficiently converted to mechanical energy to create a highly responsive, reversible, and selective sensor. This sensor responds to water, methanol, and ethanol vapors, but yields no response to either N{sub 2} or O{sub 2}. The magnitude of the signal, which is measured by a built-in piezoresistor, is correlated with the concentration and can be fitted to a Langmuir isotherm. Furthermore, we show that the hydration state of the MOF layer can be used to impart selectivity to CO{sub 2}. We also report the first use of surface-enhanced Raman spectroscopy to characterize the structure of a MOF film. We conclude that the synthetic versatility of these nanoporous materials holds great promise for creating recognition chemistries to enable selective detection of a wide range of analytes. A force field model is described that successfully predicts changes in MOF properties and the uptake of gases. This model is used to predict adsorption isotherms for a number of representative compounds, including explosives, nerve agents, volatile organic compounds, and polyaromatic hydrocarbons. The results show that, as a result of relatively large heats of adsorption (> 20 kcal mol{sup -1}) in most cases, we expect an onset of adsorption by MOF as low as 10{sup -6} kPa, suggesting the potential to detect compounds such as RDX at levels as low as 10 ppb at atmospheric pressure.

  6. Development and Test Evaluations for Ni-DOBDC Metal Organic Framework (MOF) Engineered Forms

    SciTech Connect (OSTI)

    Troy G. Garn; Mitchell Greenhalgh

    2013-07-01

    A joint effort to prepare engineered forms of a Ni-DOBDC metal organic framework (MOF) was completed with contributions from PNNL, SNL and the INL. Two independent methods were used at INL and SNL to prepare engineered form (EF) sorbents from Ni-DOBDC MOF powder developed and prepared at PNNL. Xe and Kr capacity test evaluations were performed at ambient temperature with the cryostat experimental setup at INL. The initial INL EF MOF test results indicated a Xe capacity of 1.6 mmol/kg sorbent and no Kr capacity. A large loss of surface area also occurred during minimal testing rendering the INL EF MOF unusable. Four capacity tests were completed using the SNL EF MOF at ambient temperature and resulted in Xe capacities of 1.4, 4.2, 5.0 and 3.8 mmol/kg sorbent with no Kr capacity observed in any ambient temperature tests. Two additional capacity tests were performed at 240 K to further evaluate SNL EF MOF performance. Xe capacities of 50.7 and 49.3 mmol/kg of sorbent and Kr capacities of 0.77 and 0.69 mmol/kg of sorbent were obtained, respectively. Following the adsorption evaluations, the SNL EF MOF material had lost about 40 % of the initial mass and 40 % of the initial surface area. In general, the Xe capacity results at ambient temperature for the INL and SNL EF Ni-DOBDC MOF’s were lower than 9.8 mmol Xe/kg sorbent test results reported by INL in FY-12 using PNNL’s inital EF supplied material.

  7. A coordinatively saturated sulfate encapsulated in a metal-organic framework functionalized with urea hydrogen-bonding groups

    SciTech Connect (OSTI)

    Custelcean, Radu; Moyer, Bruce A.; Hay, Benjamin P.

    2005-10-14

    A functional coordination polymer decorated with urea hydrogen-bonding donor groups has been designed for optional binding of sulfate; self-assembly of a tripodal tri-urea linker with Ag2SO4 resulted in the formation of a 1D metal-organic framework that encapsulated SO42- anions via twelve complementary hydrogen bonds, which represents the highest coordination number observed for sulfate in a natural or synthetic host.

  8. A coordinatively saturated sulfate encapsulated in a metal-organic framework functionalized with urea hydrogen-bonding groups

    SciTech Connect (OSTI)

    Custelcean, Radu; Moyer, Bruce A; Hay, Benjamin

    2005-01-01

    A functional coordination polymer decorated with urea hydrogen-bonding donor groups has been designed for optimal binding of sulfate; self-assembly of a tripodal tris-urea linker with Ag2SO4 resulted in the formation of a 1D metal - organic framework that encapsulates SO42- anions via twelve complementary hydrogen bonds, which represents the highest coordination number observed for sulfate in a natural or synthetic host.

  9. Experimental Evidence Supported by Simulations of a Very High H{sub 2} Diffusion in Metal Organic Framework Materials

    SciTech Connect (OSTI)

    Salles, F.; Maurin, G.; Jobic, H.; Koza, M. M.; Llewellyn, P. L.; Devic, T.; Serre, C.; Ferey, G.

    2008-06-20

    Quasielastic neutron scattering measurements are combined with molecular dynamics simulations to extract the self-diffusion coefficient of hydrogen in the metal organic frameworks MIL-47(V) and MIL-53(Cr). We find that the diffusivity of hydrogen at low loading is about 2 orders of magnitude higher than in zeolites. Such a high mobility has never been experimentally observed before in any nanoporous materials, although it was predicted in carbon nanotubes. Either 1D or 3D diffusion mechanisms are elucidated depending on the chemical features of the MIL framework.

  10. Carbon Dioxide Removal from Flue Gas Using Microporous Metal Organic Frameworks

    SciTech Connect (OSTI)

    Lesch, David A

    2010-06-30

    UOP LLC, a Honeywell Company, in collaboration with Professor Douglas LeVan at Vanderbilt University (VU), Professor Adam Matzger at the University of Michigan (UM), Professor Randall Snurr at Northwestern University (NU), and Professor Stefano Brandani at the University of Edinburgh (UE), supported by Honeywell's Specialty Materials business unit and the Electric Power Research Institute (EPRI), have completed a three-year project to develop novel microporous metal organic frameworks (MOFs) and an associated vacuum-pressure swing adsorption (vPSA) process for the removal of CO{sub 2} from coal-fired power plant flue gas. The project leveraged the team's complementary capabilities: UOP's experience in materials development and manufacturing, adsorption process design and process commercialization; LeVan and Brandani's expertise in high-quality adsorption measurements; Matzger's experience in syntheis of MOFs and the organic components associated with MOFs; Snurr's expertise in molecular and other modeling; Honeywell's expertise in the manufacture of organic chemicals; and, EPRI's knowledge of power-generation technology and markets. The project was successful in that a selective CO{sub 2} adsorbent with good thermal stability and reasonable contaminant tolerance was discovered, and a low cost process for flue gas CO{sub 2} capture process ready to be evaluated further at the pilot scale was proposed. The team made significant progress toward the current DOE post-combustion research targets, as defined in a recent FOA issued by NETL: 90% CO{sub 2} removal with no more than a 35% increase in COE. The team discovered that favorable CO{sub 2} adsorption at more realistic flue gas conditions is dominated by one particular MOF structure type, M/DOBDC, where M designates Zn, Co, Ni, or Mg and DOBDC refers to the form of the organic linker in the resultant MOF structure, dioxybenzenedicarboxylate. The structure of the M/DOBDC MOFs consists of infinite-rod secondary

  11. A Biomimetic Approach to New Adsorptive Hydrogen Storage Metal-Organic Frameworks

    SciTech Connect (OSTI)

    Zhou, Hongcai J

    2015-08-12

    In the past decades, there has been an escalation of interest in the study of MOFs due to their fascinating structures and intriguing application potentials. Their exceptionally high surface areas, uniform yet tunable pore sizes, and well-defined adsorbate-MOF interaction sites make them suitable for hydrogen storage. Various strategies to increase the hydrogen capacity of MOFs, such as constructing pore sizes comparable to hydrogen molecules, increasing surface area and pore volume, utilizing catenation, and introducing coordinatively unsaturated metal centers (UMCs) have been widely explored to increase the hydrogen uptake of the MOFs. MOFs with hydrogen uptake approaching the DOE gravimetric storage goal under reasonable pressure but cryo- temperature (typically 77 K) were achieved. However, the weak interaction between hydrogen molecules and MOFs has been the major hurdle limiting the hydrogen uptake of MOFs at ambient temperature. Along the road, we have realized both high surface area and strong interaction between framework and hydrogen are equally essential for porous materials to be practically applicable in Hydrogen storage. Increasing the isosteric heats of adsorption for hydrogen through the introduction of active centers into the framework could have great potential on rendering the framework with strong interaction toward hydrogen. Approaches on increasing the surface areas and improving hydrogen affinity by optimizing size and structure of the pores and the alignment of active centers around the pores in frameworks have been pursued, for example: (a) the introduction of coordinatively UMC (represents a metal center missing multiple ligands) with potential capability of multiple dihydrogen-binding (Kubas type, non-dissociative) per UMC, (b) the design and synthesis of proton-rich MOFs in which a + H3 binds dihydrogen just like a metal ion does, and (c) the preparation of MOFs and PPNs with well aligned internal electric fields. We believe the

  12. Immobilizing Highly Catalytically Active Pt Nanoparticles inside the Pores of Metal-Organic Framework: A Double Solvents Approach

    SciTech Connect (OSTI)

    Aijaz, Arshad; Karkamkar, Abhijeet J.; Choi, Young Joon; Tsumori, Nobuko; Ronnebro, Ewa; Autrey, Thomas; Shioyama, Hiroshi; Xu, Qiang

    2012-08-29

    Ultrafine Pt nanoparticles were successfully immobilized inside the pores of a metal-organic framework MIL-101 without deposition of Pt nanoparticles on the external surfaces of framework by using a 'double solvents' method. The resulting Pt@MIL-101 composites with different Pt loadings represent the first highly active MOF-immobilized metal nanocatalysts for catalytic reactions in all three phases: liquid-phase ammonia borane hydrolysis; solid-phase ammonia borane thermal dehy-drogenation and gas-phase CO oxidation. The observed excellent catalytic performances are at-tributed to the small Pt nanoparticles within the pores of MIL-101. 'We are thankful to AIST and METI for financial support. TA & AK are thankful for support from the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. PNNL is operated by Battelle.'

  13. Highly active non-PGM catalysts prepared from metal organic frameworks

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Barkholtz, Heather M.; Chong, Lina; Kaiser, Zachary B.; Xu, Tao; Liu, Di -Jia

    2015-06-11

    Finding inexpensive alternatives to platinum group metals (PGMs) is essential for reducing the cost of proton exchange membrane fuel cells (PEMFCs). Numerous materials have been investigated as potential replacements of Pt, of which the transition metal and nitrogen-doped carbon composites (TM/Nx/C) prepared from iron doped zeolitic imidazolate frameworks (ZIFs) are among the most active ones in catalyzing the oxygen reduction reaction based on recent studies. In this report, we demonstrate that the catalytic activity of ZIF-based TM/Nx/C composites can be substantially improved through optimization of synthesis and post-treatment processing conditions. Ultimately, oxygen reduction reaction (ORR) electrocatalytic activity must be demonstratedmore » in membrane-electrode assemblies (MEAs) of fuel cells. The process of preparing MEAs using ZIF-based non-PGM electrocatalysts involves many additional factors which may influence the overall catalytic activity at the fuel cell level. Evaluation of parameters such as catalyst loading and perfluorosulfonic acid ionomer to catalyst ratio were optimized. Our overall efforts to optimize both the catalyst and MEA construction process have yielded impressive ORR activity when tested in a fuel cell system.« less

  14. Highly active non-PGM catalysts prepared from metal organic frameworks

    SciTech Connect (OSTI)

    Barkholtz, Heather M.; Chong, Lina; Kaiser, Zachary B.; Xu, Tao; Liu, Di -Jia

    2015-06-11

    Finding inexpensive alternatives to platinum group metals (PGMs) is essential for reducing the cost of proton exchange membrane fuel cells (PEMFCs). Numerous materials have been investigated as potential replacements of Pt, of which the transition metal and nitrogen-doped carbon composites (TM/Nx/C) prepared from iron doped zeolitic imidazolate frameworks (ZIFs) are among the most active ones in catalyzing the oxygen reduction reaction based on recent studies. In this report, we demonstrate that the catalytic activity of ZIF-based TM/Nx/C composites can be substantially improved through optimization of synthesis and post-treatment processing conditions. Ultimately, oxygen reduction reaction (ORR) electrocatalytic activity must be demonstrated in membrane-electrode assemblies (MEAs) of fuel cells. The process of preparing MEAs using ZIF-based non-PGM electrocatalysts involves many additional factors which may influence the overall catalytic activity at the fuel cell level. Evaluation of parameters such as catalyst loading and perfluorosulfonic acid ionomer to catalyst ratio were optimized. Our overall efforts to optimize both the catalyst and MEA construction process have yielded impressive ORR activity when tested in a fuel cell system.

  15. Insights into the Temperature-Dependent “Breathing” of a Flexible Fluorinated Metal-Organic Framework

    SciTech Connect (OSTI)

    Fernandez, Carlos A.; Thallapally, Praveen K.; McGrail, B. Peter

    2012-10-08

    The framework expansion and contraction upon carbon dioxide uptake was studied in a partially fluorinated metal-organic framework, FMOF-2. The results show framework expansion and contraction (breathing) as a function of pressure and temperature. Even at temperatures as low as -30 ºC, two phase transitions seem to take place with a pressure step (corresponding to the second transition) that is greatly dependent on temperature. This behavior is described by the model proposed by Coudert and co-workers showing that the material seems to undergo two phase transitions that are temperature dependent. The isosteric heats of adsorption at high pressures show a minimum that is concurrent with the region of CO2 loadings where the second pressure step occurs. It was deduced that these lower enthalpy values are a consequence of the energy cost related to the expansion or reopening of the framework. Lastly, the large and reversible breathing behavior may be a product of the combination of the high elasticity of zinc (II) coordination and the apparent high flexibility of the V-shaped organic building block.

  16. Remote Stabilization of Copper Paddlewheel Based Molecular Building Blocks in Metal-Organic Frameworks

    SciTech Connect (OSTI)

    Gao, Wen-Yang; Cai, Rong; Pham, Tony; Forrest, Katherine A.; Hogan, Adam; Nugent, Patrick; Williams, Kia; Wojtas, Lukasz; Luebke, Ryan; Weseliinski, Lukasz J.; Zaworotko, Michael J.; Space, Brian; Chen, Yu-Sheng; Eddaoudi, Mohamed; Shi, Xiaodong; Ma, Shengqian

    2015-08-21

    Copper paddlewheel based molecular building blocks (MBBs) are ubiquitous and have been widely employed for the construction of highly porous metal–organic frameworks (MOFs). However, most copper paddlewheel based MOFs fail to retain their structural integrity in the presence of water. This instability is directly correlated to the plausible displacement of coordinating carboxylates in the copper paddlewheel MBB, [Cu₂(O₂C-)₄], by the strongly coordinating water molecules. In this comprehensive study, we illustrate the chemical stability control in the rht-MOF platform via strengthening the coordinating bonds within the triangular inorganic MBB, [Cu₃O(N4–x(CH)xC-)₃] (x = 0, 1, or 2). Remotely, the chemical stabilization propagated into the paddlewheel MBB to afford isoreticular rht-MOFs with remarkably enhanced water/chemical stabilities compared to the prototypal rht-MOF-1.

  17. Rigidifying Fluorescent Linkers by Metal-Organic Framework Formation for Fluorescence Blue Shift and Quantum Yield Enhancement

    SciTech Connect (OSTI)

    Wei, ZW; Gu, ZY; Arvapally, RK; Chen, YP; McDougald, RN; Ivy, JF; Yakovenko, AA; Feng, DW; Omary, MA; Zhou, HC

    2014-06-11

    We demonstrate that rigidifying the structure of fluorescent linkers by structurally constraining them in metal-organic frameworks (MOFs) to control their conformation effectively tunes the fluorescence energy and enhances the quantum yield. Thus, a new tetraphenylethylene-based zirconium MOF exhibits a deep-blue fluorescent emission at 470 nm with a unity quantum yield (99.9 +/- 0.5%) under Ar, representing ca. 3600 cm(-1) blue shift and doubled radiative decay efficiency vs the linker precursor. An anomalous increase in the fluorescence lifetime and relative intensity takes place upon heating the solid MOF from cryogenic to ambient temperatures. The origin of these unusual photoluminescence properties is attributed to twisted linker conformation, intramolecular hindrance, and framework rigidity.

  18. Selective Host-Guest Interaction between Metal Ions and Metal-Organic Frameworks Using Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy

    SciTech Connect (OSTI)

    Guo, Zhiyong; Kobayashi, Takeshi; Wang, Lin-Lin; Goh, Tian Wei; Xiao, Chaoxian; Caporini, Marc A.; Rosay, Melanie; Johnson, Duane D.; Pruski, Marek; Huang, Wenyu

    2014-10-08

    The host–guest interaction between metal ions (Pt²⁺ and Cu²⁺) and a zirconium metal–organic framework (UiO-66-NH₂) was explored using dynamic nuclear polarization-enhanced ¹⁵N{¹H} CPMAS NMR spectroscopy supported by X-ray absorption spectroscopy and density functional calculations. The combined experimental results conclude that each Pt²⁺ coordinates with two NH₂ groups from the MOF and two Cl⁻ from the metal precursor, whereas Cu²⁺ do not form chemical bonds with the NH₂ groups of the MOF framework. Density functional calculations reveal that Pt²⁺ prefers a square-planar structure with the four ligands and resides in the octahedral cage of the MOF in either cis or trans configurations.

  19. Selective Host-Guest Interaction between Metal Ions and Metal-Organic Frameworks using Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy

    SciTech Connect (OSTI)

    Guo, Zhiyong; Kobayashi, Takeshi; Wang, Lin-Lin; Goh, Tian Wei; Xiao, Chaoxian; Caporini, Marc A; Rosay, Melanie; Johnson, Duane D; Pruski, Marek; Huang, Wenyu

    2014-10-08

    The host–guest interaction between metal ions (Pt2+ and Cu2+) and a zirconium metal–organic framework (UiO-66-NH2) was explored using dynamic nuclear polarization-enhanced 15N{1H} CPMAS NMR spectroscopy supported by X-ray absorption spectroscopy and density functional calculations. The combined experimental results conclude that each Pt2+ coordinates with two NH2 groups from the MOF and two Cl- from the metal precursor, whereas Cu2+ do not form chemical bonds with the NH2 groups of the MOF framework. Density functional calculations reveal that Pt2+ prefers a square-planar structure with the four ligands and resides in the octahedral cage of the MOF in either cis or trans configurations.

  20. Direct Observation of Xe and Kr Adsorption in a Xe-selective Microporous Metal Organic Framework

    SciTech Connect (OSTI)

    Chen, Xianyin; Plonka, Anna M.; Banerjee, Debasis; Krishna, Rajamani; Schaef, Herbert T.; Ghose, Sanjit; Thallapally, Praveen K.; Parise, John B.

    2015-05-22

    We found that the cryogenic separation of noble gases is energy-intensive and expensive, especially when low concentrations are involved. Metal–organic frameworks (MOFs) containing polarizing groups within their pore spaces are predicted to be efficient Xe/Kr solid-state adsorbents, but no experimental insights into the nature of the Xe–network interaction are available to date. Here we report a new microporous MOF (designated SBMOF-2) that is selective toward Xe over Kr under ambient conditions, with a Xe/Kr selectivity of about 10 and a Xe capacity of 27.07 wt % at 298 K. Single-crystal diffraction results show that the Xe selectivity may be attributed to the specific geometry of the pores, forming cages built with phenyl rings and enriched with polar -OH groups, both of which serve as strong adsorption sites for polarizable Xe gas. The Xe/Kr separation in SBMOF-2 was investigated with experimental and computational breakthrough methods. These experiments showed that Kr broke through the column first, followed by Xe, which confirmed that SBMOF-2 has a real practical potential for separating Xe from Kr. Our calculations showed that the capacity and adsorption selectivity of SBMOF-2 are comparable to those of the best-performing unmodified MOFs such as NiMOF-74 or Co formate.

  1. Direct Observation of Xe and Kr Adsorption in a Xe-selective Microporous Metal Organic Framework

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Chen, Xianyin; Plonka, Anna M.; Banerjee, Debasis; Krishna, Rajamani; Schaef, Herbert T.; Ghose, Sanjit; Thallapally, Praveen K.; Parise, John B.

    2015-05-22

    We found that the cryogenic separation of noble gases is energy-intensive and expensive, especially when low concentrations are involved. Metal–organic frameworks (MOFs) containing polarizing groups within their pore spaces are predicted to be efficient Xe/Kr solid-state adsorbents, but no experimental insights into the nature of the Xe–network interaction are available to date. Here we report a new microporous MOF (designated SBMOF-2) that is selective toward Xe over Kr under ambient conditions, with a Xe/Kr selectivity of about 10 and a Xe capacity of 27.07 wt % at 298 K. Single-crystal diffraction results show that the Xe selectivity may be attributedmore » to the specific geometry of the pores, forming cages built with phenyl rings and enriched with polar -OH groups, both of which serve as strong adsorption sites for polarizable Xe gas. The Xe/Kr separation in SBMOF-2 was investigated with experimental and computational breakthrough methods. These experiments showed that Kr broke through the column first, followed by Xe, which confirmed that SBMOF-2 has a real practical potential for separating Xe from Kr. Our calculations showed that the capacity and adsorption selectivity of SBMOF-2 are comparable to those of the best-performing unmodified MOFs such as NiMOF-74 or Co formate.« less

  2. Isoreticular metal-organic frameworks, process for forming the same, and systematic design of pore size and functionality therein, with application for gas storage

    DOE Patents [OSTI]

    Yaghi, Omar M.; Eddaoudi, Mohamed; Li, Hailian; Kim, Jaheon; Rosi, Nathaniel

    2005-08-16

    An isoreticular metal-organic framework (IRMOF) and method for systematically forming the same. The method comprises the steps of dissolving at least one source of metal cations and at least one organic linking compound in a solvent to form a solution; and crystallizing the solution under predetermined conditions to form a predetermined IRMOF. At least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the organic linking compound.

  3. A Metal-Organic Framework Containing Unusual Eight-Connected Zr–-Oxo Secondary Building Units and Orthogonal Carboxylic Acids for Ultra-sensitive Metal Detection

    SciTech Connect (OSTI)

    Carboni, Michaël; Lin, Zekai; Abney, Carter W.; Zhang, Teng; Lin, Wenbin

    2015-08-21

    Two metal-organic frameworks (MOFs) with Zr-oxo secondary building units (SBUs) were prepared by using p,p'-terphenyldicarboxylate (TPDC) bridging ligands pre-functionalized with orthogonal succinic acid (MOF-1) and maleic acid groups (MOF-2). Single-crystal X-ray structure analysis of MOF-1 provides the first direct evidence for eight-connected SBUs in UiO-type MOFs. In contrast, MOF-2 contains twelve-connected SBUs as seen in the traditional UiO MOF topology. These structural assignments were confirmed by extended X-ray absorption fine structure (EXAFS) analysis. The highly porous MOF-1 is an excellent fluorescence sensor for metal ions with the detection limit of <0.5 ppb for Mn2+ and three to four orders of magnitude greater sensitivity for metal ions than previously reported luminescent MOFs.

  4. Synthesis, Structure Determination, and Hydrogen Sorption Studies of New Metal-Organic Frameworks Using Triazole and Naphthalenedicarboxylic Acid

    SciTech Connect (OSTI)

    Park,H.; Britten, J.; Mueller, U.; Lee, J.; Li, J.; Parise, J.

    2007-01-01

    Two new metal-organic framework compounds were synthesized under solvothermal conditions using Zn{sup 2+} ion, 1,2,4-triazole (TRZ), and 1,4- and 2,6-naphthalenedicarboxylic acids (NDC): Zn{sub 4}(TRZ){sub 4}(1,4-NDC){sub 2}-2DMF-2H{sub 2}O (1) and Zn{sub 4}(TRZ){sub 4}(2,6-NDC){sub 2}-2DMF-4H{sub 2}O (2). Their crystal structures were characterized by single-crystal X-ray diffraction. Structure 1 crystallizes in the P2{sub 1}/n space group with a = 13.609(2) {angstrom}, b = 27.181(5){angstrom}, c = 13.617(3) {angstrom}, {beta} = 92.46(1){sup o}, V = 5032.4(16) {angstrom}{sup 3}, and Z = 4. Structure 2 crystallizes in orthorhombic Pna2{sub 2} space group with a = 30.978(6) {angstrom}, b = 12.620(3) {angstrom}, c = 13.339(3) {angstrom}, V = 5215(2) {angstrom}{sup 3}, and Z = 4. Both structures are analogues of the previously reported Zn{sub 4}(TRZ){sub 4}(1,4-BDC){sub 2}-16H{sub 2}O where the layers of Zn-triazole moieties are pillared by aromatic dicarboxylates to create 3-D open frameworks. Nitrogen sorption studies revealed that these structures have Brunaer-Emmett-Teller (BET) surface areas of 362.1-584.1 m{sup 2}/g. Hydrogen sorption experiments showed they can store 0.84-1.09 wt % H{sub 2} at 77 K and 1 atm. Although they do not contain large pores or surface areas, they possess the hydrogen sorption capacities comparable to those of highly porous metal-organic frameworks.

  5. Graphene-wrapped sulfur/metal organic framework-derived microporous carbon composite for lithium sulfur batteries

    SciTech Connect (OSTI)

    Chen, Renjie E-mail: chenrj@bit.edu.cn; Zhao, Teng; Tian, Tian; Fairen-Jimenez, David; Cao, Shuai; Coxon, Paul R.; Xi, Kai E-mail: chenrj@bit.edu.cn; Vasant Kumar, R.; Cheetham, Anthony K.

    2014-12-01

    A three-dimensional hierarchical sandwich-type graphene sheet-sulfur/carbon (GS-S/C{sub ZIF8-D}) composite for use in a cathode for a lithium sulfur (Li-S) battery has been prepared by an ultrasonic method. The microporous carbon host was prepared by a one-step pyrolysis of Zeolitic Imidazolate Framework-8 (ZIF-8), a typical zinc-containing metal organic framework (MOF), which offers a tunable porous structure into which electro-active sulfur can be diffused. The thin graphene sheet, wrapped around the sulfur/zeolitic imidazolate framework-8 derived carbon (S/C{sub ZIF8-D}) composite, has excellent electrical conductivity and mechanical flexibility, thus facilitating rapid electron transport and accommodating the changes in volume of the sulfur electrode. Compared with the S/C{sub ZIF8-D} sample, Li-S batteries with the GS-S/C{sub ZIF8-D} composite cathode showed enhanced capacity, improved electrochemical stability, and relatively high columbic efficiency by taking advantage of the synergistic effects of the microporous carbon from ZIF-8 and a highly interconnected graphene network. Our results demonstrate that a porous MOF-derived scaffold with a wrapped graphene conductive network structure is a potentially efficient design for a battery electrode that can meet the challenge arising from low conductivity and volume change.

  6. Sulfate Separation by Selective Crystallization of a Urea-Functionalized Metal-Organic Framework

    SciTech Connect (OSTI)

    Custelcean, Radu; Sellin, Vincent; Moyer, Bruce A

    2007-01-01

    Encapsulation of SO{sub 4}{sup 2-} into a Ni coordination framework functionalized with urea anion-binding groups allows selective separation of this strongly hydrophilic anion from a highly competitive aqueous environment.

  7. Metal-Organic Framework Derived Hierarchically Porous Nitrogen-Doped Carbon Nanostructures as Novel Electrocatalyst for Oxygen Reduction Reaction

    SciTech Connect (OSTI)

    Fu, Shaofang; Zhu, Chengzhou; Zhou, Yazhou; Yang, Guohai; Jeon, Ju Won; Lemmon, John P.; Du, Dan; Nune, Satish K.; Lin, Yuehe

    2015-10-01

    The hierarchically porous nitrogen-doped carbon materials, derived from nitrogen-containing isoreticular metal-organic framework-3 (IRMOF-3) through direct carbonization, exhibited excellent electrocatalytic activity in alkaline solution for oxygen reduction reaction (ORR). This high activity is attributed to the 10 presence of high percentage of quaternary and pyridinic nitrogen, the high surface area as well as good conductivity. When IRMOF-3 was carbonized at 950 °C (CIRMOF-3-950), it showed four-electron reduction pathway for ORR and exhibited better stability (about 78.5% current density was maintained) than platinum/carbon (Pt/C) in the current durability test. In addition, CIRMOF-3-950 presented high selectivity to cathode reactions compared to commercial Pt/C.

  8. An Isoreticular Series of Metal-Organic Frameworks with Dendritic Hexacarboxylate Ligands and Exceptionally High Gas-Uptake Capacity

    SciTech Connect (OSTI)

    Yuan, Daqiang; Zhao, Dan; Sun, Daofeng; Zhou, Hong-Cai

    2010-10-01

    Metal-organic frameworks (MOFs) are newly emerging porous materials. Owing to their large surface area and tunable pore size and geometry, they have been studied for applications in gas storage and separation, especially in hydrogen and methane storage and carbon dioxide capture. It has been well established that the high-pressure gravimetric hydrogen-adsorption capacity of an MOF is directly proportional to its surface area. However, MOFs of high surface areas tend to decompose upon activation. In our previous work, we described an approach toward stable MOFs with high surface areas by incorporating mesocavities with microwindows. To extend this work, we now present an isoreticular series of (3,24)-connected MOFs made from dendritic hexacarboxylate ligands, one of which has a Langmuir surface area as high as 6033 m2 g-1. In addition, the gas-adsorption properties of this new isoreticular MOF series have been studied.

  9. Isoreticular Series of (3,24)-Connected Metal-Organic Frameworks: Facile Synthesis and High Methane Uptake Properties

    SciTech Connect (OSTI)

    Barin, G; Krungleviciute, V; Gomez-Gualdron, DA; Sarjeant, AA; Snurr, RQ; Hupp, JT; Yildirim, T; Farha, OK

    2014-03-11

    We have successfully used a highly efficient copper-catalyzed "click" reaction for the synthesis of a new series of hexacarboxylic acid linkers with varying sizes for the construction of isoreticular (3,24)-connected metal-organic frameworks (MOFs)-namely, NU-138, NU-139, and NU-140. One of these MOFs, NU-140, exhibits a gravimetric methane uptake of 0.34 g/g at 65 bar and 298 K, corresponding to almost 70% of the DOE target (0.5 g/g), and has a working capacity (deliverable amount between 65 and 5 bar) of 0.29 g/g, which translates into a volumetric working capacity of 170 cc(STP)/cc. These values demonstrate that NU-140 performs well for methane storage purposes, from both a gravimetric and a volumetric point of view. Adsorption of CO2 and H-2 along with simulated isotherms are also reported.

  10. Structure-Assisted Functional Anchor Implantation in Robust Metal-Organic Frameworks with Ultra large Pores

    SciTech Connect (OSTI)

    Park, J; Feng, DW; Zhou, HC

    2015-02-04

    A facile functionalization assisted by the structural attributes of PCN-333 has been studied while maintaining the integrity of the parent MOF including ultralarge pores, chemical robustness, and crystallinity. Herein we thoroughly analyzed ligand exchange phenomena in PCN-333 and demonstrate that the extent of exchange can be tailored by varying the exchange conditions as potential applications may require. Through this method a variety of functional groups are incorporated into PCN-333. To further show the capabilities of this system introduction of a BODIPY fluorophore as a secondary functionality was performed to the functionalized framework via a click reaction. We anticipate the PCN-333 with functional anchor can serve as a stable platform for further chemistry to be explored in future applications

  11. Rationally tuned micropores within enantiopure metal-organic frameworks for highly selective separation of acetylene and ethylene

    SciTech Connect (OSTI)

    Xiang, Sheng-Chang; Zhang, Zhangjing; Zhao, Cong-Gui; Hong, Kunlun; Zhao, Xuebo; Ding, De-Rong; Xie, Ming-Hua; Wu, Chuan-De; Madhab, Das; Gill, Rachel; Thomas, K Mark; Chen, Banglin

    2011-01-01

    Separation of acetylene and ethylene is an important industrial process because both compounds are essential reagents for a range of chemical products and materials. Current separation approaches include the partial hydrogenation of acetylene into ethylene over a supported Pd catalyst, and the extraction of cracked olefins using an organic solvent; both routes are costly and energy consuming. Adsorption technologies may allow separation, but microporous materials exhibiting highly selective adsorption of C{sub 2}H{sub 2}/C{sub 2}H{sub 4} have not been realized to date. Here, we report the development of tunable microporous enantiopure mixed-metal-organic framework (M'MOF) materials for highly selective separation of C{sub 2}H{sub 2} and C{sub 2}H{sub 4}. The high selectivities achieved suggest the potential application of microporous M'MOFs for practical adsorption-based separation of C{sub 2}H{sub 2}/C{sub 2}H{sub 4}.

  12. Oxidative homo-coupling reactions of aryl boronic acids using a porous copper metal-organic framework as a highly efficient heterogeneous catalyst

    DOE Patents [OSTI]

    Yaghi, Omar M.; Czaja, Alexander U.; Wang, Bo; Lu, Zheng

    2015-06-02

    The disclosure provides methods for the use of open metal frameworks to catalyze coupling reactions.

  13. Pore-controlled formation of 0D metal complexes in anionic 3D metal-organic frameworks

    SciTech Connect (OSTI)

    Zhang, MW; Bosch, M; Zhou, HC

    2015-01-01

    The host-guest chemistry between a series of anionic MOFs and their trapped counterions was investigated by single crystal XRD. The PCN-514 series contains crystallographically identifiable metal complexes trapped in the pores, where their formation is controlled by the size and shape of the MOF pores. A change in the structure and pore size of PCN-518 indicates that the existence of guest molecules may reciprocally affect the formation of host MOFs.

  14. A hard X-ray study of a manganese-terpyridine catalyst in a chromium-based Metal Organic Framework

    SciTech Connect (OSTI)

    Ramsey, Alexandra V.

    2015-08-28

    Hydrogen produced from water splitting is a promising source of clean energy. However, a robust catalyst is necessary to carry out the water oxidation step of water splitting. In this study, the catalyst studied was [(terpy)Mn(μ-O)2Mn(terpy)]3+ (MnTD) synthesized in the Metal Organic Framework (MOF) MIL-101(Cr), and the method used for analysis was hard X-ray powder diffraction. The diffraction data was used to detect the presence of MOF in different catalytic stages, and lattice parameters were assigned to the samples containing MOF. Fourier maps were constructed with GSAS II to determine the contents of the MOF as preliminary studies suggested that MnTD may not be present. Results showed that MOF is present before catalysis occurs but disappears by the time 45 minutes of catalysis has ensued. Changes in the MOF’s lattice parameters and location of electron density in the Fourier maps suggest attractions between the MOF and catalyst that may lead to MOF degradation. Fourier maps also revealed limited, if any, amounts of MnTD, even before catalysis occurred. Molecular manganese oxide may be the source of the high rate of water oxidation catalysis in the studied system.

  15. CO{sub 2} adsorption-based separation by metal organic framework (Cu-BTC) versus zeolite (13X)

    SciTech Connect (OSTI)

    Zhijian Liang; Marc Marshall; Alan L. Chaffee

    2009-05-15

    The potential for the metal organic framework (MOF) Cu-BTC to selectively adsorb and separate CO{sub 2} is considered. Isotherms for CO{sub 2}, CH{sub 4}, and N{sub 2} were measured from 0 to 15 bar and at temperatures between 25 and 105{sup o}C. The isotherms suggest a much higher working capacity (x4) for CO{sub 2} adsorption on Cu-BTC relative to the benchmark zeolite 13X over the same pressure range. Higher CO{sub 2}/N{sub 2} and CO{sub 2}/CH{sub 4} selectivities in the higher pressure range (1-15 bar) and with lower heats of adsorption were also demonstrated. Cu-BTC was observed to be stable in O{sub 2} at 25{sup o}C, but its crystallinity was reduced in humid environments. The CO{sub 2} adsorption capacity was progressively reduced upon cyclic exposure to water vapor at low relative humidity (<30%), but leveled out at 75% of its original value after several water adsorption/desorption cycles. 27 refs., 1 fig.

  16. Gram-scale, high-yield synthesis of a robust metal-organic framework for storing methane and other gases

    SciTech Connect (OSTI)

    Wilmer, CE; Farha, OK; Yildirim, T; Eryazici, I; Krungleviciute, V; Sarjeant, AA; Snurr, RQ; Hupp, JT

    2013-04-01

    We have synthesized and characterized a new metal-organic framework (MOF) material, NU-125, that, in the single-crystal limit, achieves a methane storage density at 58 bar (840 psi) and 298 K corresponding to 86% of that obtained with compressed natural gas tanks (CNG) used in vehicles today, when the latter are pressurized to 248 bar (3600 psi). More importantly, the deliverable capacity (58 bar to 5.8 bar) for NU-125 is 67% of the deliverable capacity of a CNG tank that starts at 248 bar. (For crystalline granules or powders, particle packing inefficiencies will yield densities and deliverable capacities lower than 86% and 67% of high-pressure CNG.) This material was synthesized in high yield on a gram-scale in a single-batch synthesis. Methane adsorption isotherms were measured over a wide pressure range (0.1-58 bar) and repeated over twelve cycles on the same sample, which showed no detectable degradation. Adsorption of CO2 and H-2 over a broad range of pressures and temperatures are also reported and agree with our computational findings.

  17. Computational Design of Metal-Organic Frameworks Based on Stable Zirconium Building Units for Storage and Delivery of Methane

    SciTech Connect (OSTI)

    Gomez-Gualdron, DA; Gutov, OV; Krungleviciute, V; Borah, B; Mondloch, JE; Hupp, JT; Yildirim, T; Farha, OK; Snurr, RQ

    2014-10-14

    A metal organic framework (MOF) with high volumetric deliverable capacity for methane was synthesized after being identified by computational screening of 204 hypothetical MOF structures featuring (Zr6O4)(OH)(4)(CO2)(n) inorganic building blocks. The predicted MOF (NU-800) has an fcu topology in which zirconium nodes are connected via ditopic 1,4-benzenedipropynoic acid linkers. Based on our computer simulations, alkyne groups adjacent to the inorganic zirconium nodes provide more efficient methane packing around the nodes at high pressures. The high predicted gas uptake properties of this new MOF were confirmed by high-pressure isotherm measurements over a large temperature and pressure range. The measured methane deliverable capacity of NU-800 between 65 and 5.8 bar is 167 cc(STP)/cc (0.215 g/g), the highest among zirconium-based MOFs. High-pressure uptake values of H-2 and CO2 are also among the highest reported. These high gas uptake characteristics, along with the expected highly stable structure of NU-800, make it a promising material for gas storage applications.

  18. Preparation of metal-triazolate frameworks

    DOE Patents [OSTI]

    Yaghi, Omar M; Uribe-Romo, Fernando J; Gandara-Barragan, Felipe; Britt, David K

    2014-10-07

    The disclosure provides for novel metal-triazolate frameworks, methods of use thereof, and devices comprising the frameworks thereof.

  19. Robust and Porous [beta]-Diketiminate-Functionalized Metal–Organic...

    Office of Scientific and Technical Information (OSTI)

    Robust and Porous beta-Diketiminate-Functionalized MetalOrganic Frameworks for Earth-A... MetalOrganic Frameworks for Earth-Abundant-Metal-Catalyzed CH Amination ...

  20. A thermodynamic tank model for studying the effect of higher hydrocarbons on natural gas storage in metal-organic frameworks

    SciTech Connect (OSTI)

    Zhang, HD; Deria, P; Farha, OK; Hupp, JT; Snurr, RQ

    2015-01-01

    Metal-organic frameworks (MOFs) are promising materials for storing natural gas in vehicular applications. Evaluation of these materials has focused on adsorption of pure methane, although commercial natural gas also contains small amounts of higher hydrocarbons such as ethane and propane, which adsorb more strongly than methane. There is, thus, a possibility that these higher hydrocarbons will accumulate in the MOF after multiple operating (adsorption/desorption) cycles, and reduce the storage capacity. To study the net effect of ethane and propane on the performance of an adsorbed natural gas (ANG) tank, we developed a mathematical model based on thermodynamics and mass balance equations that describes the state of the tank at any instant. The required inputs are the pure-component isotherms, and mixture adsorption data are calculated using the Ideal Adsorbed Solution Theory (IAST). We focused on how the "deliverable energy'' provided by the ANG tank to the engine changed over 200 operating cycles for a sample of 120 MOF structures. We found that, with any MOF, the ANG tank performance monotonically declines during early operating cycles until a "cyclic steady state'' is reached. We determined that the best materials when the fuel is 100% methane are not necessarily the best when the fuel includes ethane and propane. Among the materials tested, some top MOFs are MOF-143 > NU-800 > IRMOF-14 > IRMOF-20 > MIL-100 > NU-125 > IRMOF-1 > NU-111. MOF-143 is predicted to deliver 5.43 MJ L-1 of tank to the engine once the cyclic steady state is reached. The model also provided insights that can assist in future work to discover more promising adsorbent materials for natural gas storage.

  1. Reversible Alteration of CO2 Adsorption upon Photochemical or Thermal Treatment in a Metal-Organic Framework

    SciTech Connect (OSTI)

    Park, Jinhee; Yuan, Daqiang; Pham, Khanh T.; Li, Jian-Rong; Yakovenko, Andrey; Zhou, Hong-Cai

    2012-01-11

    A metal–organic framework (MOF) for reversible alteration of guest molecule adsorption, here carbon dioxide, upon photochemical or thermal treatment has been discovered. An azobenzene functional group, which can switch its conformation upon light irradiation or heat treatment, has been introduced to the organic linker of a MOF. The resulting MOF adsorbs different amount of CO₂ after UV or heat treatment. This remarkable stimuli-responsive adsorption effect has been demonstrated through experiments.

  2. A Porous Metal-Organic Framework with Helical Chain Building Units Exhibiting Facile Transition from Micro- to Meso-porosity

    SciTech Connect (OSTI)

    Park, Jinhee; Li, Jian-Rong; Carolina Sañudo, E.; Yuan, Daqiang; Zhou, Hong-Cai

    2012-01-01

    A metal–organic framework (MOF) with helical channels has been constructed by bridging helical chain secondary building units with 2,6-di-p-carboxyphenyl-4,4'-bipyridine ligands. The activated MOF shows permanent porosity and gas adsorption selectivity. Remarkably, the MOF exhibits a facile transition from micro- to meso-porosity.

  3. Crystal Engineering of an nbo Topology Metal-Organic Framework for Chemical Fixation of CO₂ under Ambient Conditions

    SciTech Connect (OSTI)

    Gao, Wen-Yang; Chen, Yao; Niu, Youhong; Williams, Kia; Cash, Lindsay; Perez, Pastor J.; Wojtas, Lukasz; Cai, Jianfeng; Chen, Yu-Sheng; Ma, Shengqian

    2015-02-20

    Crystal engineering of the nbo metal–organic framework (MOF) platform MOF-505 with a custom-designed azamacrocycle ligand (1,4,7,10-tetrazazcyclododecane-N,N',N'',N'''-tetra-p-methylbenzoic acid) leads to a high density of well-oriented Lewis active sites within the cuboctahedral cage in MMCF-2, [Cu₂(Cu-tactmb)(H₂O)₃(NO₃)₂]. This MOF demonstrates high catalytic activity for the chemical fixation of CO₂ into cyclic carbonates at room temperature under 1 atm pressure.

  4. Topology-guided design and syntheses of highly stable mesoporous porphyrinic zirconium metal-organic frameworks with high surface area

    SciTech Connect (OSTI)

    Liu, Tian -Fu; Feng, Dawei; Chen, Ying -Pin; Zou, Lanfang; Bosch, Mathieu; Yuan, Shuai; Wei, Zhangwen; Fordham, Stephen; Wang, Kecheng; Zhou, Hong -Cai

    2015-01-14

    Through a topology-guided strategy, a series of Zr₆-containing isoreticular porphyrinic metal–organic frameworks (MOFs), PCN-228, PCN-229, and PCN-230, with ftw-a topology were synthesized using the extended porphyrinic linkers. The bulky porphyrin ring ligand effectively prevents the network interpenetration which often appears in MOFs with increased linker length. The pore apertures of the structures range from 2.5 to 3.8 nm, and PCN-229 demonstrates the highest porosity and BET surface area among the previously reported Zr-MOFs. Additionally, by changing the relative direction of the terminal phenyl rings, this series replaces a Zr₈ cluster with a smaller Zr₆ cluster in a topologically identical framework. The high connectivity of the Zr₆ cluster yields frameworks with enhanced stability despite high porosity and ultralarge linker. As a representative example, PCN-230, constructed with the most extended porphyrinic linker, shows excellent stability in aqueous solutions with pH values ranging from 0 to 12 and demonstrates one of the highest pH tolerances among all porphyrinic MOFs. This work not only presents a successful example of rational design of MOFs with desired topology, but also provides a strategy for construction of stable mesoporous MOFs.

  5. A two-fold interpenetrating 3D metal-organic framework material constructed from helical chains linked via 4,4'-H{sub 2}bpz fragments

    SciTech Connect (OSTI)

    Xie Yiming; Zhao Zhenguo; Wu Xiaoyuan; Zhang Qisheng; Chen Lijuan; Wang Fei; Chen Shanci; Lu Canzhong

    2008-12-15

    A 3-connected dia-f-type metal-organic framework compound {l_brace}[Ag(L){sub 3/2}H{sub 2}PO{sub 4}]{r_brace}{sub n} (1) has been synthesized by self-assembly of 4,4'-H{sub 2}bpz (L=4,4'-H{sub 2}bpz=3,3',5,5'-tetramethyl-4,4'-bipyrazole) and Ag{sub 4}P{sub 2}O{sub 7} under hydrothermal conditions. It crystallizes in the tetragonal space group I4{sub 1}/acd with a=21.406(4) A, b=21.406(4) A, c=36.298(8) A, Z=32. X-ray single-crystal diffraction reveals that 1 has a three-dimensional framework with an unprecedented alternate left- and right-handed helices structure, featuring a non-uniform two-fold interpenetrated (4.14{sup 2}) net. Photoluminescent investigation reveals that the title compound displays interesting emissions in a wide region, which shows that the title compound may be a good potential candidate as a photoelectric material. - Graphical abstract: A 3-connected dia-f-type metal-organic framework compound [Ag(4,4'-bpz){sub 3/2}H{sub 2}PO{sub 4}] shows unprecedented alternating left- and right-handed helices structure, featuring a non-uniform two-fold interpenetrated (4.14{sup 2}) net.

  6. 2D?3D polycatenated and 3D?3D interpenetrated metalorganic frameworks constructed from thiophene-2,5-dicarboxylate and rigid bis(imidazole) ligands

    SciTech Connect (OSTI)

    Erer, Hakan; Ye?ilel, Okan Zafer; Ar?c?, Mrsel; Keskin, Seda; Bykgngr, Orhan

    2014-02-15

    Hydrothermal reactions of rigid 1,4-bis(imidazol-1-yl)benzene (dib) and 1,4-bis(imidazol-1-yl)-2,5-dimethylbenzene (dimb) with deprotonated thiophene-2,5-dicarboxylic acid (H{sub 2}tdc) in the presence of Zn(II) and Cd(II) salts in H{sub 2}O produced three new metalorganic frameworks, namely, [Zn(-tdc)(H{sub 2}O)(-dib)]{sub n} (1), [Cd(-tdc)(H{sub 2}O)(-dib)]{sub n} (2), and ([Cd{sub 2}({sub 3}-tdc){sub 2}(-dimb){sub 2}](H{sub 2}O)){sub n}(3). These MOFs were characterized by FT-IR spectroscopy, elemental, thermal (TG, DTA, DTG and DSC), and single-crystal X-ray diffraction analyses. Isomorphous complexes 1 and 2 reveal polycatenated 2D+2D?3D framework based on an undulated (4,4)-sql layer. Complex 3 exhibits a new 4-fold interpenetrating 3D framework with the point symbol of 6{sup 6}. Molecular simulations were used to assess the potentials of the complexes for H{sub 2} storage application. Moreover, these coordination polymers exhibit blue fluorescent emission bands in the solid state at room temperature. - Graphical abstract: In this study, hydrothermal reactions of rigid 1,4-bis(imidazol-1-yl)benzene (dib) and 1,4-bis(imidazol-1-yl)-2,5-dimethylbenzene (dimb) with deprotonated thiophene-2,5-dicarboxylic acid (H{sub 2}tdc) in the presence of Zn(II) and Cd(II) salts in H{sub 2}O produced three new metalorganic frameworks. Isomorphous complexes 1 and 2 reveal polycatenated 2D+2D?3D framework based on an undulated (4,4)-sql layer. Complex 3 exhibits a new 4-fold interpenetrating 3D framework with the point symbol of 6{sup 6}. Molecular simulations were used to assess the potentials of the complexes for H{sub 2} storage application. These coordination polymers exhibit blue fluorescent emission bands in the solid state at room temperature. Display Omitted - Highlights: Complexes 1 and 2 display polycatenated 2D+2D?3D framework. Complex 3 exhibits a new 4-fold interpenetrating 3D framework. Complex 1 adsorbs the highest amount of H{sub 2} at 100 bar and

  7. Highly efficient nonprecious metal catalyst prepared with metal–organic framework in a continuous carbon nanofibrous network

    SciTech Connect (OSTI)

    Shui, Jianglan; Chen, Chen; Grabstanowicz, Lauren; Zhao, Dan; Liu, Di -Jia

    2015-08-25

    Fuel cell vehicles, the only all-electric technology with a demonstrated >300 miles per fill travel range, use Pt as the electrode catalyst. The high price of Pt creates a major cost barrier for large-scale implementation of polymer electrolyte membrane fuel cells. Nonprecious metal catalysts (NPMCs) represent attractive low-cost alternatives. However, a significantly lower turnover frequency at the individual catalytic site renders the traditional carbon-supported NPMCs inadequate in reaching the desired performance afforded by Pt. Unconventional catalyst design aiming at maximizing the active site density at much improved mass and charge transports is essential for the next-generation NPMC. We report here a method of preparing highly efficient, nanofibrous NPMC for cathodic oxygen reduction reaction by electrospinning a polymer solution containing ferrous organometallics and zeolitic imidazolate framework followed by thermal activation. The catalyst offers a carbon nanonetwork architecture made of microporous nanofibers decorated by uniformly distributed high-density active sites. In a single-cell test, the membrane electrode containing such a catalyst delivered unprecedented volumetric activities of 3.3 A∙cm-3 at 0.9 V or 450 A∙cm-3 extrapolated at 0.8 V, representing the highest reported value in the literature. Improved fuel cell durability was also observed.

  8. Highly efficient nonprecious metal catalyst prepared with metal–organic framework in a continuous carbon nanofibrous network

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Shui, Jianglan; Chen, Chen; Grabstanowicz, Lauren; Zhao, Dan; Liu, Di -Jia

    2015-08-25

    Fuel cell vehicles, the only all-electric technology with a demonstrated >300 miles per fill travel range, use Pt as the electrode catalyst. The high price of Pt creates a major cost barrier for large-scale implementation of polymer electrolyte membrane fuel cells. Nonprecious metal catalysts (NPMCs) represent attractive low-cost alternatives. However, a significantly lower turnover frequency at the individual catalytic site renders the traditional carbon-supported NPMCs inadequate in reaching the desired performance afforded by Pt. Unconventional catalyst design aiming at maximizing the active site density at much improved mass and charge transports is essential for the next-generation NPMC. We report heremore » a method of preparing highly efficient, nanofibrous NPMC for cathodic oxygen reduction reaction by electrospinning a polymer solution containing ferrous organometallics and zeolitic imidazolate framework followed by thermal activation. The catalyst offers a carbon nanonetwork architecture made of microporous nanofibers decorated by uniformly distributed high-density active sites. In a single-cell test, the membrane electrode containing such a catalyst delivered unprecedented volumetric activities of 3.3 A∙cm-3 at 0.9 V or 450 A∙cm-3 extrapolated at 0.8 V, representing the highest reported value in the literature. Improved fuel cell durability was also observed.« less

  9. Benchmarking density functional theory predictions of framework structures and properties in a chemically diverse test set of metal-organic frameworks

    SciTech Connect (OSTI)

    Nazarian, Dalar; Ganesh, P.; Sholl, David S.

    2015-09-30

    We compiled a test set of chemically and topologically diverse Metal–Organic Frameworks (MOFs) with high accuracy experimentally derived crystallographic structure data. The test set was used to benchmark the performance of Density Functional Theory (DFT) functionals (M06L, PBE, PW91, PBE-D2, PBE-D3, and vdW-DF2) for predicting lattice parameters, unit cell volume, bonded parameters and pore descriptors. On average PBE-D2, PBE-D3, and vdW-DF2 predict more accurate structures, but all functionals predicted pore diameters within 0.5 Å of the experimental diameter for every MOF in the test set. The test set was also used to assess the variance in performance of DFT functionals for elastic properties and atomic partial charges. The DFT predicted elastic properties such as minimum shear modulus and Young's modulus can differ by an average of 3 and 9 GPa for rigid MOFs such as those in the test set. Moreover, we calculated the partial charges by vdW-DF2 deviate the most from other functionals while there is no significant difference between the partial charges calculated by M06L, PBE, PW91, PBE-D2 and PBE-D3 for the MOFs in the test set. We find that while there are differences in the magnitude of the properties predicted by the various functionals, these discrepancies are small compared to the accuracy necessary for most practical applications.

  10. How the guest molecules in nanoporous Zn(II) metal-organic framework can prevent agglomeration of ZnO nanoparticles

    SciTech Connect (OSTI)

    Moeinian, Maryam; Akhbari, Kamran

    2015-05-15

    The host and the apohost framework of [Zn{sub 2}(BDC){sub 2}(H{sub 2}O){sub 2}·(DMF){sub 2}]{sub n} (1·2H{sub 2}O·2DMF), (BDC{sup 2−}=benzene-1,4-dicarboxylate and DMF=N,N-Dimethylformamide), were synthesized and subsequently used for preparation of ZnO nanomaterials. With calcination of the host framework of 1·2H{sub 2}O·2DMF, ZnO nanoparticles were obtained. By the same process on the apohost framework of 1, agglomerated nanoparticles of ZnO were formed. These nano-structures were characterized by X-ray powder diffraction (XRD) and Scanning electron microscopy (SEM). These results indicate that with removal of the guest DMF and coordinated H{sub 2}O molecules from the one-dimensional channels of 1·2H{sub 2}O·2DMF, the tendency of nanoparticles to agglomerate increases and the role of this MOF in preparation of ZnO nanoparticles from this precursor was reduced. - Graphical abstract: Nano-porous zinc(II) MOF with guest DMF and coordinated H{sub 2}O molecules has been synthesized and characterized. The host and the apohost framework of it were used for preparation of ZnO nanomaterials. The role of these species in preparation of ZnO nanoparticles from the host framework is probably similar to the role of polymeric stabilizers in formation of nanoparticles. - Highlights: • Nanoparticles of ZnO were fabricated from nanoporous metal-organic framework. • The effect of guest DMF and coordinated H{sub 2}O molecules on this process was studied. • The effect of them in formation nanoparticle is similar to polymeric stabilizers.

  11. Benchmarking density functional theory predictions of framework structures and properties in a chemically diverse test set of metal-organic frameworks

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Nazarian, Dalar; Ganesh, P.; Sholl, David S.

    2015-09-30

    We compiled a test set of chemically and topologically diverse Metal–Organic Frameworks (MOFs) with high accuracy experimentally derived crystallographic structure data. The test set was used to benchmark the performance of Density Functional Theory (DFT) functionals (M06L, PBE, PW91, PBE-D2, PBE-D3, and vdW-DF2) for predicting lattice parameters, unit cell volume, bonded parameters and pore descriptors. On average PBE-D2, PBE-D3, and vdW-DF2 predict more accurate structures, but all functionals predicted pore diameters within 0.5 Å of the experimental diameter for every MOF in the test set. The test set was also used to assess the variance in performance of DFT functionalsmore » for elastic properties and atomic partial charges. The DFT predicted elastic properties such as minimum shear modulus and Young's modulus can differ by an average of 3 and 9 GPa for rigid MOFs such as those in the test set. Moreover, we calculated the partial charges by vdW-DF2 deviate the most from other functionals while there is no significant difference between the partial charges calculated by M06L, PBE, PW91, PBE-D2 and PBE-D3 for the MOFs in the test set. We find that while there are differences in the magnitude of the properties predicted by the various functionals, these discrepancies are small compared to the accuracy necessary for most practical applications.« less

  12. Preparation of metal-catecholate frameworks

    DOE Patents [OSTI]

    Yaghi, Omar M.; Gandara-Barragan, Felipe; Lu, Zheng; Wan, Shun

    2014-06-03

    The disclosure provides for metal catecholate frameworks, and methods of use thereof, including gas separation, gas storage, catalysis, tunable conductors, supercapacitors, and sensors.

  13. Research Update: A hafnium-based metal-organic framework as a catalyst for regioselective ring-opening of epoxides with a mild hydride source

    SciTech Connect (OSTI)

    Stephenson, Casey J.; Hassan Beyzavi, M.; Klet, Rachel C.; Hupp, Joseph T. E-mail: o-farha@northwestern.edu; Farha, Omar K. E-mail: o-farha@northwestern.edu

    2014-12-01

    Reaction of styrene oxide with sodium cyanoborohydride and a catalytic amount of Hf-NU-1000 yields the anti-Markovnikov product, 2-phenylethanol, with over 98% regioselectivity. On the other hand, propylene oxide is ring opened in a Markovnikov fashion to form 2-propanol with 95% regioselectivity. Both styrene oxide and propylene oxide failed to react with sodium cyanoborohydride without the addition of Hf-NU-1000 indicative of the crucial role of Hf-NU-1000 as a catalyst in this reaction. To the best of our knowledge, this is the first report of the use of a metal-organic framework material as a catalyst for ring-opening of epoxides with hydrides.

  14. Water-Stable Zirconium-Based Metal-Organic Framework Material with High-Surface Area and Gas-Storage Capacities

    SciTech Connect (OSTI)

    Gutov, OV; Bury, W; Gomez-Gualdron, DA; Krungleviciute, V; Fairen-Jimenez, D; Mondloch, JE; Sarjeant, AA; Al-Juaid, SS; Snurr, RQ; Hupp, JT; Yildirim, T; Farha, OK

    2014-08-14

    We designed, synthesized, and characterized a new Zr-based metal-organic framework material, NU-1100, with a pore volume of 1.53 ccg(-1) and Brunauer-Emmett-Teller (BET) surface area of 4020 m(2)g(-1); to our knowledge, currently the highest published for Zr-based MOFs. CH4/CO2/H-2 adsorption isotherms were obtained over a broad range of pressures and temperatures and are in excellent agreement with the computational predictions. The total hydrogen adsorption at 65 bar and 77 K is 0.092 gg(-1), which corresponds to 43 gL(-1). The volumetric and gravimetric methane-storage capacities at 65 bar and 298 K are approximately 180 v(STP)/v and 0.27 gg(-1), respectively.

  15. A 3D chiral metal-organic framework based on left-handed helices containing 3-amino-1 H-1,2,4-triazole ligand

    SciTech Connect (OSTI)

    Liu, Bing; Yang, Tian-Yi; Feng, Hui-Jun; Zhang, Zong-Hui; Xu, Ling

    2015-10-15

    A chiral metal-organic framework, [Cu(atr)(OH)]·0.5H{sub 2}O·0.5en (1) (Hatr=3-amino-1 H-1,2,4-triazole, en=ethylenediamine), was constructed via diffusion reaction of the achiral Hatr ligand and CuSO{sub 4} as starting materials. Compound 1 crystallizes in the chiral space group P3{sub 2}21 and features a porous metal-organic framework with 44.1% solvent-accessible volume fabricated by left-handed helices with a pitch height of l{sub p}=10.442 Å. Six helices gather around in a cycle forming a large honeycomb channel with a 6.58 Å inner diameter. Cu(II) center and atr{sup ‒} ligand regarded as 3-connected nodes, compound 1 can be simplified to a 3-c uninodal (4.12{sup 2}) (qtz-h) topological network. A gradual decreasing in the magnetic moment depending on temperature decreasing indicates an antiferromagnetic interaction in 1. The powder XRD confirms the bulk sample is a single crystal pure phase, and the thermogravimetric analysis shows the thermal stability of 1 is up to ca. 240 °C. - Highlights: • The present 3D chiral MOF is built from achiral Hatr ligand. • Six left-handed helices gather into a honeycomb channel in chiral sp P3{sub 2}21. • Compound 1 shows a 3-c uninodal (4.12{sup 2}) or qtz-h topological network. • Compound 1 indicates an antiferromagnetic interaction.

  16. High compressibility of a flexible metal–organic framework

    SciTech Connect (OSTI)

    Serra-Crespo P.; Stavitski E.; Kapteijn, F.; Gascon, J.

    2012-03-22

    The metal-organic framework NH{sub 2}-MIL-53(In) shows a very high amorphization resistance (>20 GPa) together with a large compressibility (K{sub 0} = 10.9 GPa).

  17. Understanding the Adsorption Mechanism of Xe and Kr in a Metal-Organic Framework from X-ray Structural Analysis and First- Principles Calculations

    SciTech Connect (OSTI)

    Ghose, Sanjit K.; Li, Yan; Yakovenko, Andrey; Dooryhee, Eric; Ehm, Lars; Ecker, Lynne E.; Dippel, Ann-Christin; Halder, Gregory J.; Strachan, Denis M.; Thallapally, Praveen K.

    2015-04-16

    Enhancement of adsorption capacity and separation of radioactive Xe/Kr at room temperature and above is a challenging problem. Here, we report a detailed structural refinement and analysis of the synchrotron X-ray powder diffraction data of Ni-DODBC metal organic framework with in situ Xe and Kr adsorption at room temperature and above. Our results reveal that Xe and Kr adsorb at the open metal sites, with adsorption geometries well reproduced by DFT calculations. The measured temperature-dependent adsorption capacity of Xe is substantially larger than that for Kr, indicating the selectivity of Xe over Kr and is consistent with the more negative adsorption energy (dominated by van der Waals dispersion interactions) predicted from DFT. Our results reveal critical structural and energetic information about host–guest interactions that dictate the selective adsorption mechanism of these two inert gases, providing guidance for the design and synthesis of new MOF materials for the separation of environmentally hazardous gases from nuclear reprocessing applications.

  18. Assessing electronic structure approaches for gas-ligand interactions in metal-organic frameworks: The CO{sub 2}-benzene complex

    SciTech Connect (OSTI)

    Witte, Jonathon; Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 ; Neaton, Jeffrey B.; Head-Gordon, Martin; Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720

    2014-03-14

    Adsorption of gas molecules in metal-organic frameworks is governed by many factors, the most dominant of which are the interaction of the gas with open metal sites, and the interaction of the gas with the ligands. Herein, we examine the latter class of interaction in the context of CO{sub 2} binding to benzene. We begin by clarifying the geometry of the CO{sub 2}benzene complex. We then generate a benchmark binding curve using a coupled-cluster approach with single, double, and perturbative triple excitations [CCSD(T)] at the complete basis set (CBS) limit. Against this ?CCSD(T)/CBS standard, we evaluate a plethora of electronic structure approximations: Hartree-Fock, second-order Mller-Plesset perturbation theory (MP2) with the resolution-of-the-identity approximation, attenuated MP2, and a number of density functionals with and without different empirical and nonempirical van der Waals corrections. We find that finite-basis MP2 significantly overbinds the complex. On the other hand, even the simplest empirical correction to standard density functionals is sufficient to bring the binding energies to well within 1 kJ/mol of the benchmark, corresponding to an error of less than 10%; PBE-D in particular performs well. Methods that explicitly include nonlocal correlation kernels, such as VV10, vdW-DF2, and ?B97X-V, perform with similar accuracy for this system, as do ?B97X and M06-L.

  19. Topological evolution and photoluminescent properties of a series of divalent zinc-based metalorganic frameworks tuned via ancillary ligating spacers

    SciTech Connect (OSTI)

    Lian, Xiao-Min; Zhao, Wen; Zhao, Xiao-Li

    2013-04-15

    The combination of divalent zinc ions, 4-(4-carboxybenzamido)benzoic acid and exo-bidendate bipyridine ligands gave rise to a series of new MOFs: [ZnL(bipy)]DMFH{sub 2}O (1), [ZnL(bpe)]1.5H{sub 2}O (2), [ZnL(bpa)]4H{sub 2}O (3) and [ZnL(bpp)]1.75H{sub 2}O (4) (MOF=metal-organic framework, bipy=4,4?-bipyridine, bpe=trans-1,2-bis(4-pyridyl)ethylene, bpa=1,2-bis(4-pyridinyl)ethane, bpp=1,3-bis(4-pyridinyl)propane, H{sub 2}L=4,4?-(carbonylimino)dibenzoic acid). Fine tune over the topology of the MOFs was achieved via systematically varying the geometric length of the second ligating bipyridine ligands. Single-crystal X-ray analysis reveals that complex 1 has a triply interpenetrated three-dimensional (3D) framework with elongated primitive cubic topology, whereas isostructural complexes 2 and 3 each possesses a 6-fold interpenetrated diamondiod 3D framework. Further expansion of the length of the bipyridine ligand to bpp leads to the formation of 4, which features an interesting entangled architecture of 2D?3D parallel polycatenation. In addition, the thermogravimetric analyses and solid-state photoluminescent properties of the selected complexes are investigated. - Graphical abstract: The incorporation of exo-bidendate bipyridine spacers into the ZnH{sub 2}L system has yielded a series of new MOFs exhibiting topological evolution from 3-fold interpenetration to 6-fold interpenetration and 2D?3D parallel polycatenation. Highlights: ? The effect of the pyridyl-based spacers on the formation of MOFs was explored. ? Fine tune over the topology of the MOFs was achieved. ? An interesting structure of 2D?3D parallel polycatenation is reported.

  20. High Throughput Combinatorial Screening of Biometic Metal-Organic...

    Broader source: Energy.gov (indexed) [DOE]

    miaminrelparilla.pdf (1.38 MB) More Documents & Publications High-Throughput Methodology for Discovery of Metal-Organic Frameworks with a High Binding Energy (New Joint ...

  1. Isoreticular metal-organic frameworks, process for forming the same, and systematic design of pore size and functionality therein, with application for gas storage

    DOE Patents [OSTI]

    Yaghi, Omar M.; Eddaoudi, Mohamed; Li, Hailian; Kim, Jaheon; Rosi, Nathaniel

    2007-03-27

    The ability to design and construct solid-state materials with pre-determined structures is a grand challenge in chemistry. An inventive strategy based on reticulating metal ions and organic carboxylate links into extended networks has been advanced to a point that has allowed the design of porous structures in which pore size and functionality can be varied systematically. MOF-5, a prototype of a new class of porous materials and one that is constructed from octahedral Zn--O--C clusters and benzene links, was used to demonstrate that its 3-D porous system can be functionalized with the organic groups, --Br, --NH2, --OC3H7, --OC5H11, --H4C2, and --H4C4, and its pore size expanded with the long molecular struts biphenyl, tetrahydropyrene, pyrene, and terphenyl. The ability to direct the formation of the octahedral clusters in the presence of a desired carboxylate link is an essential feature of this strategy, which resulted in the design of an isoreticular (having the same framework topology) series of sixteen well-defined materials whose crystals have open space representing up to 91.1% of the crystal volume, and homogeneous periodic pores that can be incrementally varied from 3.8 to 28.8 angstroms. Unlike the unpredictable nature of zeolite and other molecular sieve syntheses, the deliberate control exercised at the molecular level in the design of these crystals is expected to have tremendous implications on materials properties and future technologies. Indeed, data indicate that members of this series represent the first monocrystalline mesoporous organic/inorganic frameworks, and exhibit the highest capacity for methane storage (155 cm3/cm3 at 36 atm) and the lowest densities (0.41 to 0.21 g/cm3) attained to date for any crystalline material at room temperature.

  2. Prospective life-cycle modeling of a carbon capture and storage system using metal-organic frameworks for CO2 capture

    SciTech Connect (OSTI)

    Sathre, R; Masanet, E

    2013-01-01

    Metal-organic frameworks (MOFs) are promising new material media for carbon dioxide (CO2) capture. Their tunable adsorption patterns may allow relatively efficient separation of gases, e.g. from power plant exhaust. Here we conduct scenario-based prospective life-cycle system modeling to estimate the potentials and implications of large-scale MOF application for post-combustion carbon capture and storage (CCS), and estimate the source and magnitude of uncertainties. The methodological approach includes parametric system modeling to quantify relations between system components; scenario projections of plausible pathways for system scale-up; proxy data on analogous materials and processes; and uncertainty analysis of parameter significance. We estimate the system-wide material and energy flows and economic costs associated with projected large-scale CCS deployment. We compare the performance of a MOF-based system to currently more mature amine-based capture technology. We discuss balancing two critical factors that determine the success of CO2 capture media: thermodynamic efficiency of the capture/regeneration cycle, and life-cycle embodied energy and cost of the material and its ancillary systems.

  3. A Hard X-ray Study of a Manganese-Terpyridine Dimer Catalyst in a Chromium-based Metal Organic Framework - Oral Presentation

    SciTech Connect (OSTI)

    Ramsey, Alexandra

    2015-08-25

    Cleaner forms of energy are needed, and H2 produced from water spliFng is a possible source. However, a robust catalyst is necessary to carry out the water oxidaKon reacKon. Plants uKlize Photosystem II to catalyze water oxidaKon as a part of photosynthesis, and many syntheKc water oxidaKon catalysts use Photosystem II as a model. In this study, the catalyst of interest was [(terpy)Mn(μ-O)2Mn(terpy)]3+ (MnTD), which was synthesized in a chromium-based Metal Organic Framework (MOF) to avoid degradaKon of MnTD molecules. Hard X-ray powder diffracKon was the primary method of analysis. The diffracKon data was used to detect the presence of MOF in samples at different catalyKc stages, and laFce parameters were assigned to the samples containing MOF. Fourier maps were constructed to determine the contents of the MOF as preliminary studies suggested that MnTD may not be present. Results showed that MOF is present before catalysis occurs, but disappears in the iniKal stages of catalysis. Changes in the MOF’s laFce parameters suggest aWracKve interacKons between the MOF and catalyst; these interacKons may lead to the observed MOF degradaKon. Fourier maps also reveal limited, if any, amounts of MnTD in the system. Molecular manganese oxide may be the source of the high rate of water oxidaKon catalysis in the studied system.

  4. Adsorption and Separation of Light Gases on an Amino-Functionalized MetalOrganic Framework: An Adsorption and In Situ XRD Study

    SciTech Connect (OSTI)

    Couck S.; Stavitski E.; Gobehiya, E.; Kirschhock, C.E.A.; Serra-Crespo, P.; Juan-Alcaniz, J.; Martinez Joaristi, A.; Gascon, J.; Kapteijn, F.; Baron, G. V.; Denayer J.F.M.

    2012-02-29

    The NH{sub 2}-MIL-53(Al) metal-organic framework was studied for its use in the separation of CO{sub 2} from CH{sub 4}, H{sub 2}, N{sub 2} C{sub 2}H{sub 6} and C{sub 3}H{sub 8} mixtures. Isotherms of methane, ethane, propane, hydrogen, nitrogen, and CO{sub 2} were measured. The atypical shape of these isotherms is attributed to the breathing properties of the material, in which a transition from a very narrow pore form to a narrow pore form and from a narrow pore form to a large pore form occurs, depending on the total pressure and the nature of the adsorbate, as demonstrated by in-situ XRD patterns measured during adsorption. Apart from CO{sub 2}, all tested gases interacted weakly with the adsorbent. As a result, they are excluded from adsorption in the narrow pore form of the material at low pressure. CO{sub 2} interacted much more strongly and was adsorbed in significant amounts at low pressure. This gives the material excellent properties to separate CO{sub 2} from other gases. The separation of CO{sub 2} from methane, nitrogen, hydrogen, or a combination of these gases has been demonstrated by breakthrough experiments using pellets of NH{sub 2}-MIL-53(Al). The effect of total pressure (1-30 bar), gas composition, temperature (303-403 K) and contact time has been examined. In all cases, CO{sub 2} was selectively adsorbed, whereas methane, nitrogen, and hydrogen nearly did not adsorb at all. Regeneration of the adsorbent by thermal treatment, inert purge gas stripping, and pressure swing has been demonstrated. The NH{sub 2}-MIL-53(Al) pellets retained their selectivity and capacity for more than two years.

  5. CO2 Induced Phase Transitions in Diamine-Appended Metal-Organic...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    CO2 Induced Phase Transitions in Diamine-Appended Metal-Organic Frameworks Previous Next List ... study the effect of CO2 adsorption in an amine functionalized metal-organic framework. ...

  6. Cooperative Insertion of CO2 in Diamine-Appended Metal-Organic...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Insertion of CO2 in Diamine-Appended Metal-Organic Frameworks Previous Next List Thomas M. ... The results provide a mechanistic framework for designing highly efficient adsorbents ...

  7. Interpenetration as a Mechanism for Negative Thermal Expansion in the Metal-Organic Framework Cu3(btb)2 (MOF-14)

    SciTech Connect (OSTI)

    Wu, Yue; Peterson, Vanessa K.; Luks, Emily; Darwish, Tamim A.; Kepert, Cameron J.

    2014-07-11

    Metal–organic framework materials (MOFs) have recently been shown in some cases to exhibit strong negative thermal expansion (NTE) behavior, while framework interpenetration has been found to reduce NTE in many materials. Using powder and single-crystal diffraction methods we investigate the thermal expansion behavior of interpenetrated Cu3(btb)2 (MOF-14) and find that it exhibits an anomalously large NTE effect. Temperature-dependent structural analysis shows that, contrary to other interpenetrated materials, in MOF-14 the large positive thermal expansion of weak interactions that hold the interpenetrating networks together results in a low-energy contractive distortion of the overall framework structure, demonstrating a new mechanism for NTE.

  8. Interplay of Metalloligand and Organic Ligand to Tune Micropores within Isostructural Mixed-Metal Organic Frameworks (M MOFs) for Their Highly Selective Separation of Chiral and Achiral Small Molecules

    SciTech Connect (OSTI)

    Madhab, Das; He, Yabing; Kim, Jaheon; Guo, Qunsheng; Zhao, Cong-Gui; Hong, Kunlun; Xiang, Sheng-Chang; Zhang, Zhangjing; Thomas, K Mark; Krishna, Rajamani; Chen, Banglin

    2012-01-01

    Four porous isostructural mixed-metal-organic frameworks (M'MOFs) have been synthesized and structurally characterized. The pores within these M'MOFs are systematically tuned by the interplay of both the metalloligands and organic ligands which have enabled us not only to direct their highly selective separation of chiral alcohols 1-phenylethanol (PEA), 2-butanol (BUT), and 2-pentanol (2-PEN) with the highest ee up to 82.4% but also to lead highly selective separation of achiral C{sub 2}H{sub 2}/C{sub 2}H{sub 4} separation. The potential application of these M'MOFs for the fixed bed pressure swing adsorption (PSA) separation of C{sub 2}H{sub 2}/C{sub 2}H{sub 4} has been further examined and compared by the transient breakthrough simulations in which the purity requirement of 40 ppm in the outlet gas can be readily fulfilled by the fixed bed M'MOF-4a adsorber at ambient conditions.

  9. Mixed-Matric Membranes for CO2 and H2 Gas Separations Using Metal-Organic Framework and Mesoporus Hybrid Silicas

    SciTech Connect (OSTI)

    Inga Musselman; Kenneth Balkus, Jr.; John Ferraris

    2009-01-07

    In this work, we have investigated the separation performance of polymer-based mixed-matrix membranes containing metal-organic frameworks and mesoporous hybrid silicas. The MOF/Matrimid{reg_sign} and MOP-18/Matrimid{reg_sign} membranes exhibited improved dispersion and mechanical strength that allowed high additive loadings with reduced aggregation, as is the case of the 80 wt% MOP-18/Matrimid{reg_sign} and the 80% (w/w) Cu-MOF/Matrimid{reg_sign} membranes. Membranes with up to 60% (w/w) ZIF-8 content exhibited similar mechanical strength and improved dispersion. The H{sub 2}/CO{sub 2} separation properties of MOF/Matrimid{reg_sign} mixed-matrix membranes was improved by either keeping the selectivity constant and increasing the permeability (MOF-5, Cu-MOF) or by improving both selectivity and permeability (ZIF-8). In the case of MOF-5/Matrimid{reg_sign} mixed-matrix membranes, the H{sub 2}/CO{sub 2} selectivity was kept at 2.6 and the H{sub 2} permeability increased from 24.4 to 53.8 Barrers. For the Cu-MOF/Matrimid{reg_sign} mixed-matrix membranes, the H{sub 2}/CO{sub 2} selectivity was kept at 2.05 and the H{sub 2} permeability increased from 17.1 to 158 Barrers. These two materials introduced porosity and uniform paths that enhanced the gas transport in the membranes. When ZIF-8/Matrimid{reg_sign} mixed-matrix membranes were studied, the H{sub 2}/CO{sub 2} selectivity increased from 2.9 to 4.4 and the permeability of H{sub 2} increased from 26.5 to 35.8 Barrers. The increased H{sub 2}/CO{sub 2} selectivity in ZIF-8/Matrimid{reg_sign} membranes was explained by the sieving effect introduced by the ZIF-8 crystals (pore window 0.34 nm) that restricted the transport of molecules larger than H{sub 2}. Materials with microporous and/or mesoporous cavities like carbon aerogel composites with zeolite A and zeolite Y, and membranes containing mesoporous ZSM-5 showed sieving effects for small molecules (e.g. H{sub 2} and CO{sub 2}), however, the membranes were most

  10. Oxidation of ethane to ethanol by N2O in a metal-organic framework with coordinatively unsaturated iron(II) sites

    SciTech Connect (OSTI)

    Xiao, Dianne J.; Bloch, Eric D.; Mason, Jarad A.; Queen, Wendy L.; Hudson, Matthew R.; Planas, Nora; Borycz, Joshua; Dzubak, Allison L.; Verma, Pragya; Lee, Kyuho; Bonino, Francesca; Crocellà, Valentina; Yano, Junko; Bordiga, Silvia; Truhlar, Donald G.; Gagliardi, Laura; Brown, Craig M.; Long, Jeffrey R.

    2014-08-19

    Enzymatic haem and non-haem high-valent iron–oxo species are known to activate strong C–H bonds, yet duplicating this reactivity in a synthetic system remains a formidable challenge. Although instability of the terminal iron–oxo moiety is perhaps the foremost obstacle, steric and electronic factors also limit the activity of previously reported mononuclear iron(IV)–oxo compounds. In particular, although nature's non-haem iron(IV)–oxo compounds possess high-spin S = 2 ground states, this electronic configuration has proved difficult to achieve in a molecular species. These challenges may be mitigated within metal–organic frameworks that feature site-isolated iron centres in a constrained, weak-field ligand environment. Here, we show that the metal–organic framework Fe2(dobdc) (dobdc4- = 2,5-dioxido-1,4-benzenedicarboxylate) and its magnesium-diluted analogue, Fe0.1Mg1.9(dobdc), are able to activate the C–H bonds of ethane and convert it into ethanol and acetaldehyde using nitrous oxide as the terminal oxidant. Electronic structure calculations indicate that the active oxidant is likely to be a high-spin S = 2 iron(IV)–oxo species.

  11. A Robust Metal-Organic Framework with An Octatopic Ligand for Gas Adsorption and Separation: A Combined Characterization by Experiments and Molecular Simulations

    SciTech Connect (OSTI)

    Zhuang, Wenjuan; Yuan, Daqiang; Liu, Dahuan; Zhong, Chongli; Li, Jian-Rong; Zhou, Hong-Cai

    2012-01-10

    A newly designed octatopic carboxylate ligand, tetrakis[(3,5-dicarboxyphenyl)oxamethyl]methane (TDM8–) has been used to connect a dicopper paddlewheel building unit affording a metal–organic framework (MOF), Cu₄(H₂O)₄(TDM)·xS (PCN-26·xS, S represents noncoordinated solvent molecules, PCN = porous coordination network) with novel structure, high gas uptake, and interesting gas adsorption selectivity. PCN-26 contains two different types of cages, octahedral and cuboctahedral, to form a polyhedron-stacked three-dimensional framework with open channels in three orthogonal directions. Gas adsorption studies of N₂, Ar, and H₂ on an activated PCN-26 at 77 K, 1 bar, reveals a Langmuir surface area of 2545 m²/g, a Brunauer–Emmett–Teller (BET) surface area of 1854 m²/g, a total pore volume of 0.84 cm³/g, and a H₂ uptake capacity of 2.57 wt %. Additionally, PCN-26 exhibits a CO₂/N₂ selectivity of 49:1 and CO₂/CH₄ selectivity of 8.4:1 at 273 K. To investigate properties of gas adsorption and the adsorption sites for CO₂ in activated PCN-26, theoretical simulations of the adsorption isotherms of CO₂, CH₄, and N₂ at different temperatures were carried out. Experimental results corroborate very well with those of molecular simulations.

  12. Recent advances in carbon dioxide capture with metal-organic...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Recent advances in carbon dioxide capture with metal-organic frameworks Previous Next List ... Great progress in MOF materials for CO2 capture has been made in the past and reviewed ...

  13. Direct Measurement of Adsorbed Gas Redistribution in Metal-Organic...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Direct Measurement of Adsorbed Gas Redistribution in Metal-Organic Frameworks Previous Next List Ying-Pin Chen, Yangyang Liu, Dahuan Liu, Mathieu Bosch, and Hong-Cai Zhou, J. Am....

  14. Organic metal neutron detector

    DOE Patents [OSTI]

    Butler, M.A.; Ginley, D.S.

    1984-11-21

    A device for detection of neutrons comprises: as an active neutron sensing element, a conductive organic polymer having an electrical conductivity and a cross-section for said neutrons whereby a detectable change in said conductivity is caused by impingement of said neutrons on the conductive organic polymer which is responsive to a property of said polymer which is altered by impingement of said neutrons on the polymer; and means for associating a change in said alterable property with the presence of neutrons at the location of said device.

  15. Microporous Metal Organic Materials for Hydrogen Storage

    SciTech Connect (OSTI)

    S. G. Sankar; Jing Li; Karl Johnson

    2008-11-30

    We have examined a number of Metal Organic Framework Materials for their potential in hydrogen storage applications. Results obtained in this study may, in general, be summarized as follows: (1) We have identified a new family of porous metal organic framework materials with the compositions M (bdc) (ted){sub 0.5}, {l_brace}M = Zn or Co, bdc = biphenyl dicarboxylate and ted = triethylene diamine{r_brace} that adsorb large quantities of hydrogen ({approx}4.6 wt%) at 77 K and a hydrogen pressure of 50 atm. The modeling performed on these materials agree reasonably well with the experimental results. (2) In some instances, such as in Y{sub 2}(sdba){sub 3}, even though the modeling predicted the possibility of hydrogen adsorption (although only small quantities, {approx}1.2 wt%, 77 K, 50 atm. hydrogen), our experiments indicate that the sample does not adsorb any hydrogen. This may be related to the fact that the pores are extremely small or may be attributed to the lack of proper activation process. (3) Some samples such as Zn (tbip) (tbip = 5-tert butyl isophthalate) exhibit hysteresis characteristics in hydrogen sorption between adsorption and desorption runs. Modeling studies on this sample show good agreement with the desorption behavior. It is necessary to conduct additional studies to fully understand this behavior. (4) Molecular simulations have demonstrated the need to enhance the solid-fluid potential of interaction in order to achieve much higher adsorption amounts at room temperature. We speculate that this may be accomplished through incorporation of light transition metals, such as titanium and scandium, into the metal organic framework materials.

  16. Selective Binding of O(2) over N(2) in a Redox-Active Metal-Organic Framework with Open Iron(II) Coordination Sites

    SciTech Connect (OSTI)

    Bloch, Eric D.; Murray, Leslie J.; Queen, Wendy L.; Chavan, Sachin; Maximoff, Sergey N.; Bigi, Julian P.; Krishna, Rajamani; Peterson, Vanessa K.; Grandjean, Fernande; Long, Gary J.; Smit, Berend; Bordiga, Silvia; Brown, Craig M.; Long, Jeffrey R.

    2011-09-21

    The air-free reaction between FeCl₂ and H₄dobdc (dobdc{sup 4–} = 2,5-dioxido-1,4-benzenedicarboxylate) in a mixture of N,N-dimethylformamide (DMF) and methanol affords Fe₂(dobdc)·4DMF, a metal–organic framework adopting the MOF-74 (or CPO-27) structure type. The desolvated form of this material displays a Brunauer–Emmett–Teller (BET) surface area of 1360 m²/g and features a hexagonal array of one-dimensional channels lined with coordinatively unsaturated Fe{sup II} centers. Gas adsorption isotherms at 298 K indicate that Fe₂(dobdc) binds O₂ preferentially over N₂, with an irreversible capacity of 9.3 wt %, corresponding to the adsorption of one O₂ molecule per two iron centers. Remarkably, at 211 K, O₂ uptake is fully reversible and the capacity increases to 18.2 wt %, corresponding to the adsorption of one O₂ molecule per iron center. Mössbauer and infrared spectra are consistent with partial charge transfer from iron(II) to O₂ at low temperature and complete charge transfer to form iron(III) and O₂{sup 2–} at room temperature. The results of Rietveld analyses of powder neutron diffraction data (4 K) confirm this interpretation, revealing O₂ bound to iron in a symmetric side-on mode with d{sub O–O} = 1.25(1) Å at low temperature and in a slipped side-on mode with dO–O = 1.6(1) Å when oxidized at room temperature. Application of ideal adsorbed solution theory in simulating breakthrough curves shows Fe₂(dobdc) to be a promising material for the separation of O₂ from air at temperatures well above those currently employed in industrial settings.

  17. Metal-doped organic foam

    DOE Patents [OSTI]

    Rinde, James A.

    1982-01-01

    Organic foams having a low density and very small cell size and method for producing same in either a metal-loaded or unloaded (nonmetal loaded) form are described. Metal-doped foams are produced by soaking a polymer gel in an aqueous solution of desired metal salt, soaking the gel successively in a solvent series of decreasing polarity to remove water from the gel and replace it with a solvent of lower polarity with each successive solvent in the series being miscible with the solvents on each side and being saturated with the desired metal salt, and removing the last of the solvents from the gel to produce the desired metal-doped foam having desired density cell size, and metal loading. The unloaded or metal-doped foams can be utilized in a variety of applications requiring low density, small cell size foam. For example, rubidium-doped foam made in accordance with the invention has utility in special applications, such as in x-ray lasers.

  18. CO2 Induced Phase Transitions in Diamine-Appended Metal-Organic...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    CO2 Induced Phase Transitions in Diamine-Appended Metal-Organic Frameworks Previous Next List Vlaisavljevich, Bess; Odoh, Samuel O.; Schnell, Sondre K.; Dzubak, Allison; Lee,...

  19. Guest-induced emergent properties in Metal–Organic Frameworks

    SciTech Connect (OSTI)

    Allendorf, Mark D.; Foster, Michael E.; Léonard, François; Stavila, Vitalie; Feng, Patrick L.; Doty, F. Patrick; Leong, Kirsty; Ma, Eric Yue; Johnston, Scott R.; Talin, A. Alec; Shen, Zhi -Xun

    2015-03-19

    Metal–Organic frameworks (MOFs) are crystalline nanoporous materials comprised of organic electron donors linked to metal ions by strong coordination bonds. Applications such as gas storage and separations are currently receiving considerable attention, but if the unique properties of MOFs could be extended to electronics, magnetics, and photonics, the impact on material science would greatly increase. Recently, we obtained “emergent properties,” such as electronic conductivity and energy transfer, by infiltrating MOF pores with “guest” molecules that interact with the framework electronic structure. In this Perspective, we define a path to emergent properties based on the Guest@MOF concept, using zinc-carboxylate and copper-paddlewheel MOFs for illustration. Energy transfer and light harvesting are discussed for zinc carboxylate frameworks infiltrated with triplet-scavenging organometallic compounds and thiophene- and fullerene-infiltrated MOF-177. In addition, we discuss the mechanism of charge transport in TCNQ-infiltrated HKUST-1, the first MOF with electrical conductivity approaching conducting organic polymers. Lastly, these examples show that guest molecules in MOF pores should be considered not merely as impurities or analytes to be sensed but also as an important aspect of rational design.

  20. Guest-induced emergent properties in Metal–Organic Frameworks

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Allendorf, Mark D.; Foster, Michael E.; Léonard, François; Stavila, Vitalie; Feng, Patrick L.; Doty, F. Patrick; Leong, Kirsty; Ma, Eric Yue; Johnston, Scott R.; Talin, A. Alec; et al

    2015-03-19

    Metal–Organic frameworks (MOFs) are crystalline nanoporous materials comprised of organic electron donors linked to metal ions by strong coordination bonds. Applications such as gas storage and separations are currently receiving considerable attention, but if the unique properties of MOFs could be extended to electronics, magnetics, and photonics, the impact on material science would greatly increase. Recently, we obtained “emergent properties,” such as electronic conductivity and energy transfer, by infiltrating MOF pores with “guest” molecules that interact with the framework electronic structure. In this Perspective, we define a path to emergent properties based on the Guest@MOF concept, using zinc-carboxylate and copper-paddlewheelmore » MOFs for illustration. Energy transfer and light harvesting are discussed for zinc carboxylate frameworks infiltrated with triplet-scavenging organometallic compounds and thiophene- and fullerene-infiltrated MOF-177. In addition, we discuss the mechanism of charge transport in TCNQ-infiltrated HKUST-1, the first MOF with electrical conductivity approaching conducting organic polymers. Lastly, these examples show that guest molecules in MOF pores should be considered not merely as impurities or analytes to be sensed but also as an important aspect of rational design.« less

  1. Corrosion control of metals by organic coatings

    SciTech Connect (OSTI)

    Ooij, W.J. van; Bierwagen, G.P.; Skerry, B.S.; Mills, D.

    1999-01-01

    The authors present a comprehensive treatment of the entire field of corrosion control of metals, from mechanisms and testing procedures to modification of metal surfaces and interfaces by silanes and plasma techniques. They discuss the new, sophisticated analytical tools, such as Time-of-Flight SIMS and electrochemical impedance spectroscopy, and all materials -- metals, pretreatments, and paint systems. The contents include: (1) Corrosion under organic coatings; (2) Mechanisms of corrosion control by organic coatings; (3) Metal pretreatments; (4) Techniques to study organic coating-metal interfaces; (5) Modification of metal surfaces and interfaces; (6) corrosion testing; (7) Adhesion testing; (8) Paint systems; (9) Conclusions and prospects references.

  2. Method of stripping metals from organic solvents

    DOE Patents [OSTI]

    Todd, Terry A.; Law, Jack D.; Herbst, R. Scott; Romanovskiy, Valeriy N.; Smirnov, Igor V.; Babain, Vasily A.; Esimantovski, Vyatcheslav M.

    2009-02-24

    A new method to strip metals from organic solvents in a manner that allows for the recycle of the stripping agent. The method utilizes carbonate solutions of organic amines with complexants, in low concentrations, to strip metals from organic solvents. The method allows for the distillation and reuse of organic amines. The concentrated metal/complexant fraction from distillation is more amenable to immobilization than solutions resulting from current practice.

  3. Recent progress in the synthesis of metal–organic frameworks

    SciTech Connect (OSTI)

    Sun, Yujia; Zhou, Hong -Cai

    2015-09-25

    Metal–organic frameworks (MOFs) have attracted considerable attention for various applications due to their tunable structure, porosity and functionality. In general, MOFs have been synthesized from isolated metal ions and organic linkers under hydrothermal or solvothermal conditions via one-spot reactions. The emerging precursor approach and kinetically tuned dimensional augmentation strategy add more diversity to this field. In addition, to speed up the crystallization process and create uniform crystals with reduced size, many alternative synthesis routes have been explored. Recent advances in microwave-assisted synthesis and electrochemical synthesis are presented in this review. In recent years, post-synthetic approaches have been shown to be powerful tools to synthesize MOFs with modified functionality, which cannot be attained via de novo synthesis. In this study, some current accomplishments of post-synthetic modification (PSM) based on covalent transformations and coordinative interactions as well as post-synthetic exchange (PSE) in robust MOFs are provided.

  4. Recent progress in the synthesis of metal–organic frameworks

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Sun, Yujia; Zhou, Hong -Cai

    2015-09-25

    Metal–organic frameworks (MOFs) have attracted considerable attention for various applications due to their tunable structure, porosity and functionality. In general, MOFs have been synthesized from isolated metal ions and organic linkers under hydrothermal or solvothermal conditions via one-spot reactions. The emerging precursor approach and kinetically tuned dimensional augmentation strategy add more diversity to this field. In addition, to speed up the crystallization process and create uniform crystals with reduced size, many alternative synthesis routes have been explored. Recent advances in microwave-assisted synthesis and electrochemical synthesis are presented in this review. In recent years, post-synthetic approaches have been shown to bemore » powerful tools to synthesize MOFs with modified functionality, which cannot be attained via de novo synthesis. In this study, some current accomplishments of post-synthetic modification (PSM) based on covalent transformations and coordinative interactions as well as post-synthetic exchange (PSE) in robust MOFs are provided.« less

  5. Crystalline Microporous Metal-Organic Frameworks: Opportunities...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    and other photophysical properties will be discussed. bio: Mircea Dinc was born in Romania and obtained his bachelor's degree in Chemistry from Princeton University in 2003. He ...

  6. Selective Binding of O2 over N2 in a Redox-Active Metal-Organic...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Selective Binding of O2 over N2 in a Redox-Active Metal-Organic Framework with Open Iron(II) Coordination Sites Previous Next List E. D. Bloch, L. J. Murray, W. L. Queen, S. ...

  7. Cooperative Insertion of CO2 in Diamine-Appended Metal-Organic...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Cooperative Insertion of CO2 in Diamine-Appended Metal-Organic Frameworks Previous Next List Thomas M. McDonald, Jarad A. Mason, Xueqian Kong, Eric D. Bloch, David Gygi, Alessandro...

  8. 3D Covalent Organic Framework Materials database (Dataset) |...

    Office of Scientific and Technical Information (OSTI)

    Citation Details In-Document Search Title: 3D Covalent Organic Framework Materials ... DOE Contract Number: AC02-05CH11231 Resource Type: Dataset Data Type: Numeric Data ...

  9. Design and Synthesis of Nucleobase-Incorporated Metal-Organic...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Design and Synthesis of Nucleobase-Incorporated Metal-Organic Materials Previous Next List ... Design and Synthesis of Nucleobase-Incorporated Metal-Organic Materials. Inorg. Chem. ...

  10. A Reversible Crystallinity-Preserving Phase Transition in Metal...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Reversible Crystallinity-Preserving Phase Transition in Metal-Organic Frameworks: Discovery, ... was discovered in a metal-organic framework (MOF) PCN-526. During the phase ...

  11. A Versatile Synthetic Route for the Preparation of Titanium Metal...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    A Versatile Synthetic Route for the Preparation of Titanium Metal-Organic Frameworks ... A Versatile Synthetic Route for the Preparation of Titanium Metal-Organic Frameworks. ...

  12. CO2 induced phase transitions in diamine-appended metal–organic frameworks

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Vlaisavljevich, Bess; Odoh, Samuel O.; Schnell, Sondre K.; Dzubak, Allison L.; Lee, Kyuho; Planas, Nora; Neaton, Jeffrey B.; Gagliardi, Laura; Smit, Berend

    2015-06-17

    Using a combination of density functional theory and lattice models, we study the effect of CO2 adsorption in an amine functionalized metal–organic framework. These materials exhibit a step in the adsorption isotherm indicative of a phase change. The pressure at which this step occurs is not only temperature dependent but is also metal center dependent. Likewise, the heats of adsorption vary depending on the metal center. Herein we demonstrate via quantum chemical calculations that the amines should not be considered firmly anchored to the framework and we explore the mechanism for CO2 adsorption. An ammonium carbamate species is formed viamore » the insertion of CO2 into the M–Namine bonds. Furthermore, we translate the quantum chemical results into isotherms using a coarse grained Monte Carlo simulation technique and show that this adsorption mechanism can explain the characteristic step observed in the experimental isotherm while a previously proposed mechanism cannot. Furthermore, metal analogues have been explored and the CO2 binding energies show a strong metal dependence corresponding to the M–Namine bond strength. We show that this difference can be exploited to tune the pressure at which the step in the isotherm occurs. Additionally, the mmen–Ni2(dobpdc) framework shows Langmuir like behavior, and our simulations show how this can be explained by competitive adsorption between the new model and a previously proposed model.« less

  13. CO2 induced phase transitions in diamine-appended metal–organic frameworks

    SciTech Connect (OSTI)

    Vlaisavljevich, Bess; Odoh, Samuel O.; Schnell, Sondre K.; Dzubak, Allison L.; Lee, Kyuho; Planas, Nora; Neaton, Jeffrey B.; Gagliardi, Laura; Smit, Berend

    2015-06-17

    Using a combination of density functional theory and lattice models, we study the effect of CO2 adsorption in an amine functionalized metal–organic framework. These materials exhibit a step in the adsorption isotherm indicative of a phase change. The pressure at which this step occurs is not only temperature dependent but is also metal center dependent. Likewise, the heats of adsorption vary depending on the metal center. Herein we demonstrate via quantum chemical calculations that the amines should not be considered firmly anchored to the framework and we explore the mechanism for CO2 adsorption. An ammonium carbamate species is formed via the insertion of CO2 into the M–Namine bonds. Furthermore, we translate the quantum chemical results into isotherms using a coarse grained Monte Carlo simulation technique and show that this adsorption mechanism can explain the characteristic step observed in the experimental isotherm while a previously proposed mechanism cannot. Furthermore, metal analogues have been explored and the CO2 binding energies show a strong metal dependence corresponding to the M–Namine bond strength. We show that this difference can be exploited to tune the pressure at which the step in the isotherm occurs. Additionally, the mmen–Ni2(dobpdc) framework shows Langmuir like behavior, and our simulations show how this can be explained by competitive adsorption between the new model and a previously proposed model.

  14. A single crystalline porphyrinic titanium metal–organic framework

    SciTech Connect (OSTI)

    Yuan, Shuai; Liu, Tian -Fu; Feng, Dawei; Tian, Jian; Wang, Kecheng; Qin, Junsheng; Zhang, Qiang; Chen, Ying -Pin; Bosch, Mathieu; Zou, Lanfang; Teat, Simon J.; Dalgarno, Scott J.; Zhou, Hong -Cai

    2015-04-28

    We successfully assembled the photocatalytic titanium-oxo cluster and photosensitizing porphyrinic linker into a metal–organic framework (MOF), namely PCN-22. A preformed titanium-oxo carboxylate cluster is adopted as the starting material to judiciously control the MOF growth process to afford single crystals. This synthetic method is useful to obtain highly crystalline titanium MOFs, which has been a daunting challenge in this field. Moreover, PCN-22 demonstrated permanent porosity and photocatalytic activities toward alcohol oxidation.

  15. Bi–Mn mixed metal organic oxide: A novel 3d-6p mixed metal coordination network

    SciTech Connect (OSTI)

    Shi, Fa-Nian; Rosa Silva, Ana; Bian, Liang

    2015-05-15

    A new terminology of metal organic oxide (MOO) was given a definition as a type of coordination polymers which possess the feature of inorganic connectivity between metals and the direct bonded atoms and show 1D, 2D or 3D inorganic sub-networks. One such compound was shown as an example. A 3d-6p (Mn–Bi. Named MOOMnBi) mixed metals coordination network has been synthesized via hydrothermal method. The new compound with the molecular formula of [MnBi{sub 2}O(1,3,5-BTC){sub 2}]{sub n} (1,3,5-BTC stands for benzene-1,3,5-tricarboxylate) was characterized via single crystal X-ray diffraction technique that revealed a very interesting 3-dimensional (3D) framework with Bi{sub 4}O{sub 2}(COO){sub 12} clusters which are further connected to Mn(COO){sub 6} fragments into a 2D MOO. The topology study indicates an unprecedented topological type with the net point group of (4{sup 13}.6{sup 2})(4{sup 13}.6{sup 8})(4{sup 16}.6{sup 5})(4{sup 18}.6{sup 10})(4{sup 22}.6{sup 14})(4{sup 3}) corresponding to 3,6,7,7,8,9-c hexa-nodal net. MOOMnBi shows catalytic activity in the synthesis of (E)-α,β-unsaturated ketones. - Graphical abstract: This metal organic framework (MOF) is the essence of a 2D metal organic oxide (MOO). - Highlights: • New concept of metal organic oxide (MOO) was defined and made difference from metal organic framework. • New MOO of MOOMnBi was synthesized by hydrothermal method. • Crystal structure of MOOMnBi was determined by single crystal X-ray analysis. • The catalytic activity of MOOMnBi was studied showing reusable after 2 cycles.

  16. Biomimicry in metal-organic materials

    SciTech Connect (OSTI)

    Zhang, MW; Gu, ZY; Bosch, M; Perry, Z; Zhou, HC

    2015-06-15

    Nature has evolved a great number of biological molecules which serve as excellent constructional or functional units for metal-organic materials (MOMs). Even though the study of biomimetic MOMs is still at its embryonic stage, considerable progress has been made in the past few years. In this critical review, we will highlight the recent advances in the design, development and application of biomimetic MOMs, and illustrate how the incorporation of biological components into MOMs could further enrich their structural and functional diversity. More importantly, this review will provide a systematic overview of different methods for rational design of MOMs with biomimetic features. Published by Elsevier B.V.

  17. Metal-doped organic gels and method thereof

    DOE Patents [OSTI]

    Satcher, Jr., Joe H.; Baumann, Theodore F.

    2007-10-23

    Disclosed herein is a sol-gel polymerization process for synthesizing metal-doped organic gels. The process polymerizes metal salts of hydroxylated benzenes or hydroxylated benzene derivatives with alkyl or aryl aldehydes to form metal-doped, wet, organic gels. The gels can then be dried by supercritical solvent extraction to form metal-doped aerogels or by evaporation to form metal-doped xerogels. The aerogels and xerogels can then be pyrolyzed.

  18. Metal-doped organic gels and method thereof

    DOE Patents [OSTI]

    Satcher, Jr., Joe H.; Baumann, Theodore F.

    2003-09-02

    Disclosed herein is a sol-gel polymerization process for synthesizing metal-doped organic gels. The process polymerizes metal salts of hydroxylated benzenes or hydroxylated benzene derivatives with alkyl or aryl aldehydes to form metal-doped, wet, organic gels. The gels can then be dried by supercritical solvent extraction to form metal-doped aerogels or by evaporation to form metal-doped xerogels. The aerogels and xerogels can then be pyrolyzed.

  19. Metal-Organic Heat Carrier Nanofluids

    SciTech Connect (OSTI)

    McGrail, B. Peter; Thallapally, Praveen K.; Blanchard, Jeremy; Nune, Satish K.; Jenks, Jeromy WJ; Dang, Liem X.

    2013-09-01

    Nanofluids, dispersions of metal or oxide nanoparticles in a base working fluid, are being intensively studied due to improvements they offer in thermal properties of the working fluid. However, these benefits have been erratically demonstrated and proven impacts on thermal conductivity are modest and well described from long-established effective medium theory. In this paper, we describe a new class of metal-organic heat carrier (MOHC) nanofluid that offers potential for a larger performance boost in thermal vapor-liquid compression cycles. MOHCs are nanophase porous coordination solids designed to reversibly uptake the working fluid molecules in which the MOHCs are suspended. Additional heat can be extracted in a heat exchanger or solar collector from the endothermic enthalpy of desorption, which is then released as the nanofluid transits through a power generating device such as a turboexpander. Calculations for an R123 MOHC nanofluid indicated potential for up to 15% increase in power output. Capillary tube experiments show that liquid-vapor transitions occur without nanoparticle deposition on the tube walls provided entrance Reynolds number exceeds approximately 100.

  20. Design and synthesis of nucleobase-incorporated metal-organic...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Design and synthesis of nucleobase-incorporated metal-organic materials Previous Next List ... This work also offers a general perspective for the design and synthesis of ...

  1. Structural and property studies on metal-organic compounds with...

    Office of Scientific and Technical Information (OSTI)

    with 3-D supramolecular network Citation Details In-Document Search Title: Structural and property studies on metal-organic compounds with 3-D supramolecular network Two ...

  2. Ten new predicted covalent organic frameworks with strong optical response in the visible and near infrared

    SciTech Connect (OSTI)

    Yang, Li-Ming E-mail: ganzx001@umn.edu; Frauenheim, Thomas; Dornfeld, Matthew; Hui, Pik-Mai; Ganz, Eric E-mail: ganzx001@umn.edu

    2015-06-28

    We use density functional theory to predict and evaluate 10 novel covalent organic frameworks (COFs), labeled (X{sub 4}Y)(BDC){sub 3}, (X = C/Si; Y = C, Si, Ge, Sn, and Pb), with topology based on metal organic framework isoreticular metal-organic framework (IRMOF-1), but with new elements substituted for the corner atoms. We show that these new materials are stable structures using frequency calculations. For two structures, (C{sub 4}C and Si{sub 4}C) molecular dynamics simulations were performed to demonstrate stability of the systems up to 600 K for 10 ps. This demonstrates the remarkable stability of these systems, some of which may be experimentally accessible. For the C{sub 4}C material, we also explored the stability of isolated corners and linkers and vacuum and started to build the structure from these pieces. We discuss the equilibrium lattice parameters, formation enthalpies, electronic structures, chemical bonding, and mechanical and optical properties. The predicted bulk moduli of these COFs range from 18.9 to 23.9 GPa, larger than that of IRMOF-1 (ca. 15.4 GPa), and larger than many existing 3D COF materials. The band gaps range from 1.5 to 2.1 eV, corresponding to 600–830 nm wavelength (orange through near infrared). The negative values of the formation enthalpy suggest that they are stable and should be experimentally accessible under suitable conditions. Seven materials distort the crystal structure to a lower space group symmetry Fm-3, while three materials maintain the original Fm-3m space group symmetry. All of the new materials are highly luminescent. We hope that this work will inspire efforts for experimental synthesis of these new materials.

  3. Tuning the Topology and Functionality of Metal–Organic Frameworks by Ligand Design

    SciTech Connect (OSTI)

    Zhao, Dan; Timmons, Daren J; Yuan, Daqiang; Zhou, Hong-Cai

    2011-02-15

    Metal–organic frameworks (MOFs)—highly crystalline hybrid materials that combine metal ions with rigid organic ligands—have emerged as an important class of porous materials. The organic ligands add flexibility and diversity to the chemical structures and functions of these materials. In this Account, we summarize our laboratory’s experience in tuning the topology and functionality of MOFs by ligand design. These investigations have led to new materials with interesting properties. By using a ligand that can adopt different symmetry conformations through free internal bond rotation, we have obtained two MOFs that are supramolecular stereoisomers of each other at different reaction temperatures. In another case, where the dimerized ligands function as a D₃-Piedfort unit spacer, we achieve chiral (10,3)-a networks. In the design of MOF-based materials for hydrogen and methane storage, we focused on increasing the gas affinity of frameworks by using ligands with different geometries to control the pore size and effectively introduce unsaturated metal centers (UMCs) into the framework. Framework interpenetration in PCN-6 (PCN stands for porous coordination network) can lead to higher hydrogen uptake. Because of the proper alignment of the UMCs, PCN-12 holds the record for uptake of hydrogen at 77 K/760 Torr. In the case of methane storage, PCN-14 with anthracene-derived ligand achieves breakthrough storage capacity, at a level 28% higher than the U.S. Department of Energy target. Selective gas adsorption requires a pore size comparable to that of the target gas molecules; therefore, we use bulky ligands and network interpenetration to reduce the pore size. In addition, with the help of an amphiphilic ligand, we were able to use temperature to continuously change pore size in a 2D layer MOF. Adding charge to an organic ligand can also stabilize frameworks. By ionizing the amine group within mesoMOF-1, the resulting electronic repulsion keeps the network from

  4. Single-Crystal Structure of a Covalent Organic Framework

    SciTech Connect (OSTI)

    Zhang, YB; Su, J; Furukawa, H; Yun, YF; Gandara, F; Duong, A; Zou, XD; Yaghi, OM

    2013-11-06

    The crystal structure of a new covalent organic framework, termed COF-320, is determined by single-crystal 3D electron diffraction using the rotation electron diffraction (RED) method for data collection. The COF crystals are prepared by an imine condensation of tetra-(4-anilyl)methane and 4,4'-biphenyldialdehyde in 1,4-dioxane at 120 degrees C to produce a highly porous 9-fold interwoven diamond net. COF-320 exhibits permanent porosity with a Langmuir surface area of 2400 m(2)/g and a methane total uptake of 15.0 wt % (176 cm(3)/cm(3)) at 25 degrees C and 80 bar. The successful determination of the structure of COF-320 directly from single-crystal samples is an important advance in the development of COF chemistry.

  5. Microporous metal organic framework [M{sub 2}(hfipbb){sub 2}(ted)] (M=Zn, Co; H{sub 2}hfipbb=4,4-(hexafluoroisopropylidene)-bis(benzoic acid); ted=triethylenediamine): Synthesis, structure analysis, pore characterization, small gas adsorption and CO{sub 2}/N{sub 2} separation properties

    SciTech Connect (OSTI)

    Xu, William W.; Pramanik, Sanhita; Zhang, Zhijuan; Emge, Thomas J.; Li, Jing

    2013-04-15

    Carbon dioxide is a greenhouse gas that is a major contributor to global warming. Developing methods that can effectively capture CO{sub 2} is the key to reduce its emission to the atmosphere. Recent research shows that microporous metal organic frameworks (MOFs) are emerging as a promising family of adsorbents that may be promising for use in adsorption based capture and separation of CO{sub 2} from power plant waste gases. In this work we report the synthesis, crystal structure analysis and pore characterization of two microporous MOF structures, [M{sub 2}(hfipbb){sub 2}(ted)] (M=Zn (1), Co (2); H{sub 2}hfipbb=4,4-(hexafluoroisopropylidene)-bis(benzoic acid); ted=triethylenediamine). The CO{sub 2} and N{sub 2} adsorption experiments and IAST calculations are carried out on [Zn{sub 2}(hfipbb){sub 2}(ted)] under conditions that mimic post-combustion flue gas mixtures emitted from power plants. The results show that the framework interacts with CO{sub 2} strongly, giving rise to relatively high isosteric heats of adsorption (up to 28 kJ/mol), and high adsorption selectivity for CO{sub 2} over N{sub 2}, making it promising for capturing and separating CO{sub 2} from CO{sub 2}/N{sub 2} mixtures. - Graphical abstract: Microporous [Zn{sub 2}(hfipbb){sub 2}(ted)] demonstrates high adsorption selectivity for CO{sub 2} over N{sub 2} under conditions that mimic flue gas mixtures. Highlights: ► Two new porous MOFs were synthesized and characterized by rational design. ► The small pore size leads to greatly enhanced CO{sub 2}–MOF interaction. ► High adsorption selectivity of the Zn–MOF for CO{sub 2} over N{sub 2} is achieved.

  6. Photochemical deterioration of the organic/metal contacts in organic optoelectronic devices

    SciTech Connect (OSTI)

    Wang Qi; Williams, Graeme; Aziz, Hany; Tsui Ting

    2012-09-15

    We study the effect of exposure to light on a wide range of organic/metal contacts that are commonly used in organic optoelectronic devices and found that irradiation by light in the visible and UV range results in a gradual deterioration in their electrical properties. This photo-induced contact degradation reduces both charge injection (i.e., from the metal to the organic layer) and charge extraction (i.e., from the organic layer to the metal). X-ray photoelectron spectroscopy (XPS) measurements reveal detectable changes in the interface characteristics after irradiation, indicating that the photo-degradation is chemical in nature. Changes in XPS characteristics after irradiation suggests a possible reduction in bonds associated with organic-metal complexes. Measurements of interfacial adhesion strength using the four-point flexure technique reveal a decrease in organic/metal adhesion in irradiated samples, consistent with a decrease in metal-organic bond density. The results shed the light on a new material degradation mechanism that appears to have a wide presence in organic/metal interfaces in general, and which likely plays a key role in limiting the stability of various organic optoelectronic devices such as organic light emitting devices, organic solar cells, and organic photo-detectors.

  7. Computational screening of porous metal-organic frameworks and...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Additionally, concerning the simultaneous removal of SO2, NOx, and CO2, Mg-MOF-74 gave the ... helpful to the adsorbents selection in the separation of SO2 and NOx, and carbon capture.

  8. Metal-Organic Frameworks with Precisely Designed Interior for...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    with Precisely Designed Interior for Carbon Dioxide Capture in the Presence of Water Previous Next ... breakthrough time of 610 10 s g-1 and full preservation of the MOF structure

  9. Metal-Organic Frameworks as Adsorbents for Hydrogen Purification...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Purification and Precombustion Carbon Dioxide Capture Previous Next List Z. R. Herm, J. A. ... pressures up to 40 bar for Zn4O(BTB)2 (MOF-177, BTB3- 1,3,5-benzenetribenzoate), ...

  10. Guest-Induced Electrical Conductivity in Metal-Organic Frameworks...

    Office of Scientific and Technical Information (OSTI)

    Close Cite: Bibtex Format Close 0 pages in this document matching the terms "" Search For Terms: Enter terms in the toolbar above to search the full text of this document for ...

  11. An Isoreticular Series of Metal-Organic Frameworks with Dendritic...

    Office of Scientific and Technical Information (OSTI)

    obtain a copy of this journal article from the publisher. Find in Google Scholar Find in Google Scholar Search WorldCat Search WorldCat to find libraries that may hold this journal

  12. Ultrastable Polymolybdate-Based Metal-Organic Frameworks as Highly...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    of (trim)43, NENU-5, and HKUST-1 were also studied for comparison. Remarkably, as a 3D hydrogen-evolving cathode operating in acidic electrolytes, NENU-500 exhibits the highest...

  13. Isostructural Metal-Organic Frameworks Assembled from Functionalized...

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    Assembled from Functionalized Diisophthalate Ligands through a Ligand-Truncation Strategy Previous Next List Yangyang Liu, Jian-Rong Li, Wolfgang M. Verdegaal, Tian-Fu Liu,...

  14. Stable Metal-Organic Frameworks Containing Single-Molecule Traps...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    possess great potential in chemical manufacturing, including pharmaceuticals, fuel production and food processing. However, the engineering of enzymes is severely hampered...

  15. Guest-Induced Electrical Conductivity in Metal-Organic Frameworks

    Office of Scientific and Technical Information (OSTI)

    fabrication Reconfigurable electronics Rad-hard Novel electronic material MOFs combine ... at 10 V (<10-12 A) Infiltrated MOF (trace water): s0.1 Scm, 108 increase Vibrational ...

  16. Protein Immobilization in Metal-Organic Frameworks by Covalent...

    Office of Scientific and Technical Information (OSTI)

    DOE Contract Number: SC0001015 Resource Type: Journal Article Resource Relation: ... Language: English Subject: membrane, carbon capture, materials and chemistry by design, synthesis ...

  17. Synthesis, characterization, and application of metal organic framework nanostructures

    SciTech Connect (OSTI)

    Fernandez, Carlos A.; Nune, Satish K.; Motkuri, Radha K.; Thallapally, Praveen K.; Wang, Chong M.; Liu, Jun; Exarhos, Gregory J.; McGrail, B. Peter

    2010-12-21

    Nano sized (square and cube) prussian blue analogues were synthesized using PVP, AOT and Chitosan as stabilizers at room temperature

  18. Metal-Organic Frameworks Incorporating Copper-Complexed Rotaxanes

    SciTech Connect (OSTI)

    Coskun, Ali; Hmadeh, Mohamad; Barin, Gokhan; Gándara, Felipe; Li, Qiaowei; Choi, Eunwoo; Strutt, Nathan L.; Cordes, David B.; Slawin, Alexandra M.Z.; Stoddart, J. Fraser; Sauvage, Jean-Pierre; Yaghi, Omar M.

    2013-07-26

    MOFs on the move: A copper-coordinated [2]pseudorotaxanate which reacts with zinc nitrate to form threefold interpenetrated networks retains most of its solution-state chemistry, including its ability to undergo electronic switching of some of the copper(I) ions under redox control.

  19. Confinement of Metal-Organic Polyhedra in Silica Nanopores |...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Confinement of Metal-Organic Polyhedra in Silica Nanopores Previous Next List Lin-Bing Sun, Jian-Rong Li, Weigang Lu, Zhi-Yuan Gu, Zhiping Luo, and Hong-Cai Zhou, J. Am. Chem....

  20. Strong and Reversible Binding of Carbon Dioxide in a Green Metal–Organic Framework

    SciTech Connect (OSTI)

    Gassensmith, Jeremiah J.; Furukawa, Hiroyasu; Smaldone, Ronald A.; Forgan, Ross S.; Botros, Youssry Y.; Yaghi, Omar M.; Stoddart, J. Fraser

    2011-08-30

    The efficient capture and storage of gaseous CO₂ is a pressing environmental problem. Although porous metal–organic frameworks (MOFs) have been shown to be very effective at adsorbing CO₂ selectively by dint of dipole–quadruple interactions and/or ligation to open metal sites, the gas is not usually trapped covalently. Furthermore, the vast majority of these MOFs are fabricated from nonrenewable materials, often in the presence of harmful solvents, most of which are derived from petrochemical sources. Herein we report the highly selective adsorption of CO₂ by CD-MOF-2, a recently described green MOF consisting of the renewable cyclic oligosaccharide γ-cyclodextrin and RbOH, by what is believed to be reversible carbon fixation involving carbonate formation and decomposition at room temperature. The process was monitored by solid-state ¹³C NMR spectroscopy as well as colorimetrically after a pH indicator was incorporated into CD-MOF-2 to signal the formation of carbonic acid functions within the nanoporous extended framework.

  1. Direct Measurement of Adsorbed Gas Redistribution in Metal–Organic Frameworks

    SciTech Connect (OSTI)

    Chen, Ying-Pin; Liu, Yangyang; Liu, Dahuan; Bosch, Mathieu; Zhou, Hong-Cai

    2015-03-04

    Knowledge about the interactions between gas molecules and adsorption sites is essential to customize metal-organic frameworks (MOFs) as adsorbents. The dynamic interactions occurring during adsorption/desorption working cycles with several states are especially complicated. Even so, the gas dynamics based upon experimental observations and the distribution of guest molecules under various conditions in MOFs have not been extensively studied yet. In this work, a direct time-resolved diffraction structure envelope (TRDSE) method using sequential measurements by in situ synchrotron powder X-ray diffraction has been developed to monitor several gas dynamic processes taking place in MOFs: infusion, desorption, and gas redistribution upon temperature change. The electron density maps indicate that gas molecules prefer to redistribute over heterogeneous types of sites rather than to exclusively occupy the primary binding sites. We found that the gas molecules are entropically driven from open metal sites to larger neighboring spaces during the gas infusion period, matching the localized-to-mobile mechanism. In addition, the partitioning ratio of molecules adsorbed at each site varies with different temperatures, as opposed to an invariant distribution mode. Equally important, the gas adsorption in MOFs is intensely influenced by the gas–gas interactions, which might induce more molecules to be accommodated in an orderly compact arrangement. This sequential TRDSE method is generally applicable to most crystalline adsorbents, yielding information on distribution ratios of adsorbates at each type of site.

  2. Inorganic Metal Oxide/Organic Polymer Nanocomposites And Method Thereof

    DOE Patents [OSTI]

    Gash, Alexander E.; Satcher, Joe H.; Simpson, Randy

    2004-11-16

    A synthetic method for preparation of hybrid inorganic/organic energetic nanocomposites is disclosed herein. The method employs the use of stable metal in organic salts and organic solvents as well as an organic polymer with good solubility in the solvent system to produce novel nanocomposite energetic materials. In addition, fuel metal powders (particularly those that are oxophilic) can be incorporated into composition. This material has been characterized by thermal methods, energy-filtered transmission electron microscopy (EFTEM), N.sub.2 adsoprtion/desorption methods, and Fourier-Transform (FT-IR) spectroscopy. According to these characterization methods the organic polymer phase fills the nanopores of the material, providing superb mixing of the component phases in the energetic nanocomposite.

  3. Organizing environmental flow frameworks to meet hydropower mitigation needs

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    McManamay, Ryan A.; Brewer, Shannon K.; Jager, Henriette I.; Troia, Matthew J.

    2016-06-25

    The global recognition of the importance of natural flow regimes to sustain the ecological integrity of river systems has led to increased societal pressure on the hydropower industry to change plant operations to improve downstream aquatic ecosystems. However, a complete reinstatement of natural flow regimes is often unrealistic when balancing water needs for ecosystems, energy production, and other human uses. Thus, stakeholders must identify a prioritized subset of flow prescriptions that meet ecological objectives in light of realistic constraints. Yet, isolating aspects of flow regimes to restore downstream of hydropower facilities is among the greatest challenges of environmental flow sciencemore » due, in part, to the sheer volume of available environmental flow tools in conjunction with complex negotiation-based regulatory procedures. Here, we propose an organizational framework that structures information and existing flow paradigms into a staged process that assists stakeholders in implementing environmental flows for hydropower facilities. The framework identifies areas where regulations fall short of the needed scientific process, and provide suggestions for stakeholders to ameliorate those situations through advanced preparation. We highlight the strengths of existing flow paradigms in their application to hydropower settings and suggest when and where tools are most applicable. In conclusion, our suggested framework increases the effectiveness and efficiency of the e-flow implementation process by rapidly establishing a knowledge base and decreasing uncertainty so more time can be devoted to filling knowledge gaps. As a result, the framework provides the structure for a coordinated research agenda to further the science of environmental flows related to hydropower environments.« less

  4. Crystal engineering, structure–function relationships, and the future of metal–organic frameworks

    SciTech Connect (OSTI)

    Allendorf, Mark D.; Stavila, Vitalie

    2014-10-15

    Metal-Organic Frameworks (MOFs) are a rapidly expanding class of hybrid organic-inorganic materials that can be rationally designed and assembled through crystal engineering. The explosion of interest in this subclass of coordination polymers results from their outstanding properties and myriad possible applications that include traditional uses of microporous materials, such as gas storage, separations, and catalysis, to new realms in biomedicine, electronic devices, and and information storage. The objective of this Highlight article is to provide the reader with a sense of where the field stands after roughly fifteen years of research. Remarkable progress has been made, but the barriers to practical and commercial advances are also illuminated. We discuss the basic elements of MOF assembly and present a conceptual hierarchy of structural elements that assists in understanding how unique properties in these materials can be achieved. Structure-function relationships are then discussed; several are now well understood as a result of the focused efforts of many research groups over the past decade. Prospects for practical applications of MOFs in membranes, catalysis, biomedicine, and as active components in electronic and photonic devices are also discussed. Finally, we list key challenges that, in our view, must be addressed for these materials to realize their full potential in the marketplace.

  5. Crystal engineering, structure–function relationships, and the future of metal–organic frameworks

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Allendorf, Mark D.; Stavila, Vitalie

    2014-10-15

    Metal-Organic Frameworks (MOFs) are a rapidly expanding class of hybrid organic-inorganic materials that can be rationally designed and assembled through crystal engineering. The explosion of interest in this subclass of coordination polymers results from their outstanding properties and myriad possible applications that include traditional uses of microporous materials, such as gas storage, separations, and catalysis, to new realms in biomedicine, electronic devices, and and information storage. The objective of this Highlight article is to provide the reader with a sense of where the field stands after roughly fifteen years of research. Remarkable progress has been made, but the barriers tomore » practical and commercial advances are also illuminated. We discuss the basic elements of MOF assembly and present a conceptual hierarchy of structural elements that assists in understanding how unique properties in these materials can be achieved. Structure-function relationships are then discussed; several are now well understood as a result of the focused efforts of many research groups over the past decade. Prospects for practical applications of MOFs in membranes, catalysis, biomedicine, and as active components in electronic and photonic devices are also discussed. Finally, we list key challenges that, in our view, must be addressed for these materials to realize their full potential in the marketplace.« less

  6. Assembly of new polyoxometalate–templated metal–organic frameworks based on flexible ligands

    SciTech Connect (OSTI)

    Li, Na; Mu, Bao; Lv, Lei; Huang, Rudan

    2015-03-15

    Four new polyoxometalate(POM)–templated metal–organic frameworks based on flexible ligands, namely, [Cu{sub 6}(bip){sub 12}(PMo{sup VI}{sub 12}O{sub 40}){sub 2}(PMo{sup V}Mo{sup VI}{sub 11}O{sub 40}O{sub 2})]·8H{sub 2}O(1), [Cu{sup I}{sub 3}Cu{sup II}{sub 3}(bip){sub 12}(PMo{sup VI}{sub 12}O{sub 40}){sub 2}(PMo{sup V}{sub 12}O{sub 34})]·8H{sub 2}O(2), [Ni{sub 6}(bip){sub 12}(PMo{sup VI}{sub 12}O{sub 40})(PMo{sup VI}{sub 11}Mo{sup V}O{sub 40}){sub 2}]Cl·6H{sub 2}O(3), [Co{sup II}{sub 3}Co{sup III}{sub 2}(H{sub 2}bib){sub 2}(Hbib){sub 2}(PW{sub 9}O{sub 34}){sub 2}(H{sub 2}O){sub 6}]·6H{sub 2}O(4) (bip=1,3-bis(imidazolyl)propane, bib=1,4-bis(imidazolyl)butane) have been obtained under hydrothermal condition and characterized by single-crystal X-ray diffraction analyses, elemental analyses, and thermogravimetric (TG) analyses. The studies of single crystal X-ray indicate that compounds 1–3 crystallize in the trigonal space group P-3, and compound 4 crystallizes in the triclinic space group P-1. Compounds 1 and 3 represent 3D frameworks, and POMs as the guest molecules are incorporated into the cages which are composed of the ligands and metals, while compounds 2 and 4 show 3D frameworks by hydrogen bonds. This compounds provide new examples of host–guest compounds based on flexible bis(imidazole) ligands. In addition, the electrochemical property and the catalytic property of compound 1 have also been investigated. - Graphical abstract: Four inorganic–organic hybrid compounds based polyoxometalates (POMs) and flexible ligands, namely, have been obtained under hydrothermal conditions and characterized by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, and thermogravimetric (TG) analyses. Compounds 1–3 are new examples of host–guest compounds based on flexible bis(imidazole) ligands and POMs as the guest molecules are incorporated into the cages which are composed of the ligands and metals. - Highlights: • Polyoxometalate

  7. Inorganic metal oxide/organic polymer nanocomposites and method thereof

    DOE Patents [OSTI]

    Gash, Alexander E.; Satcher, Joe H.; Simpson, Randy

    2004-03-30

    A synthetic method for preparation of hybrid inorganic/organic energetic nanocomposites is disclosed herein. The method employs the use of stable metal inorganic salts and organic solvents as well as an organic polymer with good solubility in the solvent system to produce novel nanocomposite energetic materials. In addition, fuel metal powders (particularly those that are oxophillic) can be incorporated into composition. This material has been characterized by thermal methods, energy-filtered transmission electron microscopy (EFTEM), N.sub.2 adsoprtion/desorption methods, and Fourier-Transform (FT-IR) spectroscopy. According to these characterization methods the organic polymer phase fills the nanopores of the composite material, providing superb mixing of the component phases in the energetic nanocomposite.

  8. Pressure-induced isostructural phase transition of a metal-organic framework Co2(4,4'-bpy)3(NO3)4·xH2O

    SciTech Connect (OSTI)

    Zhou, Mi; Wang, Kai; Men, Zhiwei; Sun, Chenglin; Li, Zhanlong; Liu, Bingbing; Zou, Guangtian; Zou, Bo

    2014-07-17

    Based on the 4,4'-bipyridine organic linker, metal–organic frameworks of Co2(4,4'-bpy)3(NO3)4·xH2O (CB-MOF) have been prepared. The pressure-dependent structure evolution of CB-MOF has been investigated up to 11 GPa. An isostructural phase transition was observed at about 6 GPa followed by negative compressibility along the b axis.

  9. Selectively catalytic micro- and nanocrystals of metal–organic framework [Co(4-bpdh)(HIA)]{sub ∝}

    SciTech Connect (OSTI)

    Ye, Jing; Gou, Yongxia; Xu, Zhen-Liang; Xu, Haitao

    2015-03-15

    Metal–organic framework micro-crystals [Co(4-bpdh)(HIA)]{sub ∝} (1Co), crystallized in the monoclinic system (space group P12/n1, a=10.0009(16) Å, b=15.472(3) Å, c=18.563(3) Å, β=91.81(0)°, and Z=4), were controllably synthesized through the adjustment of the solvent system. The Co{sup 2+} ion center located in a six-coordinated environment combined with 5-hydroxyisophthalic acid (HIA) to produce ladder-like structures, which again linked with 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hxadiene (4-bpdh) to yield a double-layer network. Micro-crystals 1Co exhibited selectively oxidation-catalytic properties for the degradation of methyl orange (conversion 90%) owing to ligand to metal charge transfer. Our work determined that the synthesized catalyst is not only highly selective for degradation of organic dyes, but also very efficient. - Graphical abstract: Metal–organic framework micro-crystals [Co(4-bpdh)(HIA)]{sub ∝} (1Co) were controllably synthesized through the adjustment of the solvent system. The Co{sup 2+} ion center located in a six-coordinated environment combined with the ligands to yield a double-layer network. Micro-crystals 1Co exhibited selectively catalytic properties for the degradation of methyl orange (conversion 90%) owing to ligand to metal charge transfer. - Highlights: • Synthesis and structure of metal–organic framework [Co(4-bpdh)(HIA)]{sub ∝}. • Selectively catalytic micro- and nanocrystals. • The degradation and conversion of methyl orange.

  10. SEQUESTERING AGENTS FOR ACTIVE CAPS - REMEDIATION OF METALS AND ORGANICS

    SciTech Connect (OSTI)

    Knox, A; Michael Paller, M; Danny D. Reible, D; Xingmao Ma, X; Ioana G. Petrisor, I

    2007-05-10

    This research evaluated organoclays, zeolites, phosphates, and a biopolymer as sequestering agents for inorganic and organic contaminants. Batch experiments were conducted to identify amendments and mixtures of amendments for metal and organic contaminants removal and retention. Contaminant removal was evaluated by calculating partitioning coefficients. Metal retention was evaluated by desorption studies in which residue from the removal studies was extracted with 1 M MgCl{sub 2} solution. The results indicated that phosphate amendments, some organoclays, and the biopolymer, chitosan, were very effective sequestering agents for metals in fresh and salt water. Organoclays were very effective sorbents for phenanthrene, pyrene, and benzo(a)pyrene. Partitioning coefficients for the organoclays were 3000-3500 ml g{sup -1} for benzo(a)pyrene, 400-450 ml g{sup -1} for pyrene, and 50-70 ml g{sup -1} for phenanthrene. Remediation of sites with a mixture of contaminants is more difficult than sites with a single contaminant because metals and organic contaminants have different fate and transport mechanisms in sediment and water. Mixtures of amendments (e.g., organoclay and rock phosphate) have high potential for remediating both organic and inorganic contaminants under a broad range of environmental conditions, and have promise as components in active caps for sediment remediation.

  11. Pore surface engineering in a zirconium metal–organic framework via thiol-ene reaction

    SciTech Connect (OSTI)

    Gui, Bo; Hu, Guiping; Zhou, Tailin; Wang, Cheng

    2015-03-15

    A porous olefin-functionalized Zr(IV)-based metal–organic framework, denoted as UiO-68-allyl, has been constructed. Our results clearly demonstrated that the surface of UiO-68-allyl could be decorated with organic molecule (ethanethiol) via thiol-ene reaction. More importantly, the crystallinity of the framework were maintained during the post-synthetic modification process. However, the microporosity of the framework is retained but the surface area decreased, due to the grafting of ethylthio groups into the pores. From our studies, we can conclude that the strategy of post-synthetic modification of UiO-68-allyl via thiol-ene reaction may be general. Furthermore, we may anchor other desired functional group onto the pore walls in Zr-MOFs via thiol-ene reaction, enabling more potential applications. - graphical abstract: In this manuscript, we reported the post-synthetic modification of an olefin-functionalized Zr(IV)-based metal–organic framework via thiol-ene reaction. - Highlights: • A porous olefin-functionalized Zr(IV)-based metal–organic framework has been constructed. • The surface of olefin-functionalized Zr-MOF could be decorated with organic molecules via thiol-ene reaction. • The crystallinity and permanent porosity of the framework were maintained during the post-synthetic modification process.

  12. Method of making metal-doped organic foam products

    DOE Patents [OSTI]

    Rinde, James A.

    1981-01-01

    Organic foams having a low density and very small cell size and method for roducing same in either a metal-loaded or unloaded (nonmetal loaded) form are described. Metal-doped foams are produced by soaking a polymer gel in an aqueous solution of desired metal salt, soaking the gel successively in a solvent series of decreasing polarity to remove water from the gel and replace it with a solvent of lower polarity with each successive solvent in the series being miscible with the solvents on each side and being saturated with the desired metal salt, and removing the last of the solvents from the gel to produce the desired metal-doped foam having desired density cell size, and metal loading. The unloaded or metal-doped foams can be utilized in a variety of applications requiring low density, small cell size foam. For example, rubidium-doped foam made in accordance with the invention has utility in special applications, such as in x-ray lasers.

  13. Short-Term Metal/Organic Interface Stability Investigations of Organic Photovoltaic Devices: Preprint

    SciTech Connect (OSTI)

    Reese, M. O.; Morfa, A. J.; White, M. S.; Kopidakis, N.; Shaheen, S. E.; Rumbles, G.; Ginley, D. S.

    2008-05-01

    This paper addresses one source of degradation in OPV devices: the metal/organic interface. The basic approach was to study the completed device stability vs. the stability of the organic film itself as shown in subsequent devices fabricated from the films.

  14. Structure-Assisted Functional Anchor Implantation in Robust Metal...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Structure-Assisted Functional Anchor Implantation in Robust Metal-Organic Frameworks with ... functionality was performed to the functionalized framework via a click reaction. ...

  15. Comprehensive study of carbon dioxide adsorption in the metal...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Comprehensive study of carbon dioxide adsorption in the metal-organic frameworks M2(dobdc) (M ... physisorptive interaction with the framework surface and sheds more light on the ...

  16. Use of metal organic fluors for spectral discrimination of neutrons and gammas.

    SciTech Connect (OSTI)

    Allendorf, Mark D.; Doty, F. Patrick; Feng, Patrick L.

    2010-09-01

    A new method for spectral shape discrimination (SSD) of fast neutrons and gamma rays has been investigated. Gammas interfere with neutron detection, making efficient discrimination necessary for practical applications. Pulse shape discrimination (PSD) in liquid organic scintillators is currently the most effective means of gamma rejection. The hazardous liquids, restrictions on volume, and the need for fast timing are drawbacks to traditional PSD scintillators. In this project we investigated harvesting excited triplet states to increase scintillation yield and provide distinct spectral signatures for gammas and neutrons. Our novel approach relies on metal-organic phosphors to convert a portion of the energy normally lost to the scintillation process into useful luminescence with sub-microsecond lifetimes. The approach enables independent control over delayed luminescence wavelength, intensity, and timing for the first time. We demonstrated that organic scintillators, including plastics, nanoporous framework materials, and oil-based liquids can be engineered for both PSD and SSD.

  17. Synthesis, Structure, and Metalation of Two New Highly Porous...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Synthesis, Structure, and Metalation of Two New Highly Porous Zirconium Metal-Organic Frameworks Previous Next List William Morris, Boris Volosskiy, Selcuk Demir, Felipe Gndara,...

  18. Heterobimetallic Metal–Organic Framework as a Precursor to Prepare a Nickel/Nanoporous Carbon Composite Catalyst for 4-Nitrophenol Reduction

    SciTech Connect (OSTI)

    Yang, Ying; Zhang, Ying; Sun, Cheng Jun; Li, Xinsong; Zhang, Wen; Ma, Xiaohui; Ren, Yang; Zhang, Xin

    2014-11-01

    Nickel/nanoporous carbon (Ni/NPC) composites are facilely prepared by direct pyrolysis of nonporous heterobimetallic zinc-nickel-terephthalate frameworks (Zn1-xNixMOF, x approximate to 0-1, MOF= metal-organic framework) at 1223 K in situ. Tailoring the Ni/Zn ratio creates densely populated and small Ni nanocrystals (Ni NCs) while maintaining sufficient porosity and surface area in the final product, which exhibits the largest activity factor (9.2 s(-1)g(-1)) and excellent stability toward 4-nitrophenol reduction.

  19. Composites for removing metals and volatile organic compounds and method thereof

    DOE Patents [OSTI]

    Coronado, Paul R.; Coleman, Sabre J.; Reynolds, John G.

    2006-12-12

    Functionalized hydrophobic aerogel/solid support structure composites have been developed to remove metals and organic compounds from aqueous and vapor media. The targeted metals and organics are removed by passing the aqueous or vapor phase through the composite which can be in molded, granular, or powder form. The composites adsorb the metals and the organics leaving a purified aqueous or vapor stream. The species-specific adsorption occurs through specific functionalization of the aerogels tailored towards specific metals and/or organics. After adsorption, the composites can be disposed of or the targeted metals and/or organics can be reclaimed or removed and the composites recycled.

  20. Three-dimensional periodic supramolecular organic framework ion sponge in water and microcrystals

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Tian, Jia; Zhou, Tian-You; Zhang, Shao-Chen; Aloni, Shaul; Altoe, Maria Virginia; Xie, Song-Hai; Wang, Hui; Zhang, Dan-Wei; Zhao, Xin; Liu, Yi; et al

    2014-12-02

    Self-assembly has emerged as a powerful approach to generating complex supramolecular architectures. Despite there being many crystalline frameworks reported in the solid state, the construction of highly soluble periodic supramolecular networks in a three-dimensional space is still a challenge. In this paper we demonstrate that the encapsulation motif, which involves the dimerization of two aromatic units within cucurbit[8]uril, can be used to direct the co-assembly of a tetratopic molecular block and cucurbit[8]uril into a periodic three-dimensional supramolecular organic framework in water. The periodicity of the supramolecular organic framework is supported by solution-phase small-angle X-ray-scattering and diffraction experiments. Upon evaporating themore » solvent, the periodicity of the framework is maintained in porous microcrystals. Lastly, as a supramolecular 'ion sponge', the framework can absorb different kinds of anionic guests, including drugs, in both water and microcrystals, and drugs absorbed in microcrystals can be released to water with selectivity.« less

  1. Three-dimensional periodic supramolecular organic framework ion sponge in water and microcrystals

    SciTech Connect (OSTI)

    Tian, Jia; Zhou, Tian-You; Zhang, Shao-Chen; Aloni, Shaul; Altoe, Maria Virginia; Xie, Song-Hai; Wang, Hui; Zhang, Dan-Wei; Zhao, Xin; Liu, Yi; Li, Zhan-Ting

    2014-12-02

    Self-assembly has emerged as a powerful approach to generating complex supramolecular architectures. Despite there being many crystalline frameworks reported in the solid state, the construction of highly soluble periodic supramolecular networks in a three-dimensional space is still a challenge. In this paper we demonstrate that the encapsulation motif, which involves the dimerization of two aromatic units within cucurbit[8]uril, can be used to direct the co-assembly of a tetratopic molecular block and cucurbit[8]uril into a periodic three-dimensional supramolecular organic framework in water. The periodicity of the supramolecular organic framework is supported by solution-phase small-angle X-ray-scattering and diffraction experiments. Upon evaporating the solvent, the periodicity of the framework is maintained in porous microcrystals. Lastly, as a supramolecular 'ion sponge', the framework can absorb different kinds of anionic guests, including drugs, in both water and microcrystals, and drugs absorbed in microcrystals can be released to water with selectivity.

  2. Zeolite-like metal–organic frameworks (ZMOFs): Design, synthesis, and properties

    SciTech Connect (OSTI)

    Eddaoudi, Mohamed; Sava, Dorina F.; Eubank, Jarrod F.; Adil, Karim; Guillerm, Vincent

    2015-10-24

    This study highlights various design and synthesis approaches toward the construction of ZMOFs, which are metal–organic frameworks (MOFs) with topologies and, in some cases, features akin to traditional inorganic zeolites. The interest in this unique subset of MOFs is correlated with their exceptional characteristics arising from the periodic pore systems and distinctive cage-like cavities, in conjunction with modular intra- and/or extra-framework components, which ultimately allow for tailoring of the pore size, pore shape, and properties towards specific applications.

  3. On the Thermodynamics of Framework Breathing: A Free Energy Model...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    ...jp311601q Abstract: When adsorbing guest molecules, the porous metal-organic framework MIL-53(Cr) may vary its cell parameters drastically while retaining its crystallinity. ...

  4. A mesoporous metal–organic framework based on a shape-persistent macrocycle

    SciTech Connect (OSTI)

    Chen, Teng -Hao; Popov, Ilya; Chuang, Yu -Chun; Chen, Yu -Sheng; Miljani, Ognjen S.

    2015-08-26

    A mesoporous Zn-based metal–organic framework (MOF) was prepared from a shape-persistent phenylene ethynylene macrocycle functionalized with three –COOH groups. The rigid ligand has a ~ 9 Å wide central cavity which serves as a predesigned pore. The macrocycles [ππ] stack into pairs, with their carboxylate groups connected via three Zn₃O₁₄C₆H₂ clusters. The resulting MOF has a void volume of 86%.

  5. A metal-free organic-inorganic aqueous flow battery

    SciTech Connect (OSTI)

    Huskinson, B; Marshak, MP; Suh, C; Er, S; Gerhardt, MR; Galvin, CJ; Chen, XD; Aspuru-Guzik, A; Gordon, RG; Aziz, MJ

    2014-01-08

    As the fraction of electricity generation from intermittent renewable sources-such as solar or wind-grows, the ability to store large amounts of electrical energy is of increasing importance. Solid-electrode batteries maintain discharge at peak power for far too short a time to fully regulate wind or solar power output(1,2). In contrast, flow batteries can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all of the electro-active species in fluid form(3-5). Wide-scale utilization of flow batteries is, however, limited by the abundance and cost of these materials, particularly those using redox-active metals and precious-metal electrocatalysts(6,7). Here we describe a class of energy storage materials that exploits the favourable chemical and electro-chemical properties of a family of molecules known as quinones. The example we demonstrate is ametal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid (AQDS). AQDS undergoes extremely rapid and reversible two-electron two-proton reduction on a glassy carbon electrode in sulphuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the quinone/hydroquinone couple with the Br-2/Br- redox couple, yields a peak galvanic power density exceeding 0.6 W cm(-2) at 1.3 A cm(-2). Cycling of this quinone-bromide flow battery showed >99 per cent storage capacity retention per cycle. The organic anthraquinone species can be synthesized from inexpensive commodity chemicals(8). This organic approach permits tuning of important properties such as the reduction potential and solubility by adding functional groups: for example, we demonstrate that the addition of two hydroxy groups to AQDS increases the open circuit potential of the cell by 11% and we describe a pathway for further increases in cell voltage. The use of p-aromatic redox-active organic molecules instead of redox-active metals

  6. New metal-organic nanomaterials synthesized by laser irradiation of organic liquids

    SciTech Connect (OSTI)

    Kuzmin, Stanislav L.; Wesolowski, Michal J.; Duley, Walter W.

    2014-03-31

    A new type of metal-organic composition consisting of clusters of nanoparticles has been synthesised by laser irradiation of metallocene/benzene solutions. The metallocene molecules in this reaction become the source of the metal. Exposure to high-energy femtosecond laser pulses dehydrogenate benzene molecules and initiate the high-temperature high-pressure conditions that results in the synthesis of new materials. Irradiation experiments have been carried out on ferrocene/benzene and on other solutions. With ferrocene the synthesis of a new compound has been confirmed by X-ray powder diffraction as the peaks detected do not correspond to any known substance in the Crystallography Open Database. Theoretical simulation of the periodic structure of this new carbide predicts that it has hexagonal symmetry and a unit cell with a = 3.2A and c =2.8A. The exact structure is still uncertain but may be determined from scanning tunneling microscope (STM) studies.

  7. Anisotropic thermal expansion of a 3D metal–organic framework with hydrophilic and hydrophobic pores

    SciTech Connect (OSTI)

    Kondo, Atsushi Maeda, Kazuyuki

    2015-01-15

    A 3D flexible metal–organic framework (MOF) with 1D hydrophilic and hydrophobic pores shows anisotropic thermal expansion with relatively large thermal expansion coefficient (α{sub a}=−21×10{sup −6} K{sup −1} and α{sub c}=79×10{sup −6} K{sup −1}) between 133 K and 383 K. Temperature change gives deformation of both pores, which expand in diameter and elongate in length on cooling and vice versa. The thermally induced structural change should be derived from a unique framework topology like “lattice fence”. Silica accommodation changes not only the nature of the MOF but also thermal responsiveness of the MOF. Since the hydrophobic pores in the material are selectively blocked by the silica, the MOF with the silica is considered as a hydrophilic microporous material. Furthermore, inclusion of silica resulted in a drastic pore contraction in diameter and anisotropically changed the thermal responsiveness of the MOF. - Graphical abstract: A 3D metal–organic framework with hydrophilic and hydrophobic pores shows anisotropic thermal expansion behavior. The influence of silica filler in the hydrophobic pore was investigated. - Highlights: • Thermally induced structural change of a 3D MOF with a lattice fence topology was investigated. • The structural change was analyzed by synchrotron X-ray diffraction patterns. • Temperature change induces anisotropic thermal expansion/contraction of the MOF. • Silica inclusion anisotropically changes the thermal responsiveness of the MOF.

  8. Cooperative Template-Directed Assembly of Mesoporous Metal–Organic Frameworks

    SciTech Connect (OSTI)

    Sun, Lin-Bing; Li, Jian-Rong; Park, Jinhee; Zhou, Hong-Cai

    2012-01-11

    Despite great efforts, the development of a reliable way to assemble mesoporous metal–organic frameworks (mesoMOFs) remains a challenge. In this work, we have designed a cooperative template system, comprising a surfactant (cetyltrimethylammonium bromide) and a chelating agent (citric acid), for the generation of a mesoMOF containing a hierarchical system of mesopores interconnected with microspores. The surfactant molecules form micelles and the chelating agent bridges the MOF and the micelles, making self-assembly and crystal growth proceed under the direction of the cooperative template. However, when the surfactant or the chelating agent was applied individually, no mesoMOF was obtained.

  9. High Throughput Combinatorial Screening of Biometic Metal-Organic...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Cu 2+ Ni Pd Pt SBU metal ions bare metal Carboxylate linkers Vibrational Spectroscopy of Hydrogen Raman *H 2 in gas phase is Raman active due to large polarizability ...

  10. Atomic charges for modeling metal–organic frameworks: Why and how

    SciTech Connect (OSTI)

    Hamad, Said Balestra, Salvador R.G.; Bueno-Perez, Rocio; Calero, Sofia; Ruiz-Salvador, A. Rabdel

    2015-03-15

    Atomic partial charges are parameters of key importance in the simulation of Metal–Organic Frameworks (MOFs), since Coulombic interactions decrease with the distance more slowly than van der Waals interactions. But despite its relevance, there is no method to unambiguously assign charges to each atom, since atomic charges are not quantum observables. There are several methods that allow the calculation of atomic charges, most of them starting from the electronic wavefunction or the electronic density or the system, as obtained with quantum mechanics calculations. In this work, we describe the most common methods employed to calculate atomic charges in MOFs. In order to show the influence that even small variations of structure have on atomic charges, we present the results that we obtained for DMOF-1. We also discuss the effect that small variations of atomic charges have on the predicted structural properties of IRMOF-1. - Graphical abstract: We review the different method with which to calculate atomic partial charges that can be used in force field-based calculations. We also present two examples that illustrate the influence of the geometry on the calculated charges and the influence of the charges on structural properties. - Highlights: • The choice of atomic charges is crucial in modeling adsorption and diffusion in MOFs. • Methods for calculating atomic charges in MOFs are reviewed. • We discuss the influence of the framework geometry on the calculated charges. • We discuss the influence of the framework charges on structural the properties.

  11. Selective CO 2 Capture from Flue Gas Using Metal–Organic Frameworks-A Fixed Bed Study

    SciTech Connect (OSTI)

    Liu, Jian; Tian, Jian; Thallapally, Praveen K.; McGrail, B. Peter

    2012-05-03

    It is important to capture carbon dioxide from flue gas which is considered to be the main reason to cause global warming. CO2/N2 separation by novel adsorbents is a promising method to reduce CO2 emission but effect of water and CO2/N2 selectivity is critical to apply the adsorbents into practical applications. A very well known, Metal Organic Framework, NiDOBDC (Ni-MOF-74 or CPO-27-Ni) was synthesized through a solvothermal reaction and the sample (500 to 800 microns) was used in a fixed bed CO2/N2 breakthrough study with and without H2O. The Ni/DOBDC pellet has a high CO2 capacity of 3.74 mol/kg at 0.15 bar and a high CO2/N2 selectivity of 38, which is much higher than those of reported MOFs and zeolites under dry condition. Trace amount of water can impact CO2 adsorption capacity as well as CO2/N2 selectivity for the Ni/DOBDC. However, Ni/DOBDC can retain a significant CO2 capacity and CO2/N2 selectivity at 0.15 bar CO2 with 3% RH water. These results indicate a promising future to use the Ni/DOBDC in CO2 capture from flue gas.

  12. A three-dimensional metal–organic framework for selective sensing of nitroaromatic compounds

    SciTech Connect (OSTI)

    Tian, Dan; Chen, Rong-Ying; Xu, Jian; Bu, Xian-He; Li, Yun-Wu

    2014-12-01

    A 3D metal–organic framework [NH{sub 2}(CH{sub 3}){sub 2}][Cd{sub 6}(L){sub 4}(DMF){sub 6}(HCOO)](DMF = N,N-dimethylformamide) (1) has been synthesized using a tripodal ligand H{sub 3}L (2,4,6-tris[1-(3-carboxylphenoxy)ylmethyl]mesitylene). The obtained complex exhibits a 3D framework containing hexanuclear (Cd{sub 6}) building units formed by two trinuclear (Cd{sub 3}) clusters that are connected via HCOO{sup −} anions. For complex 1, the participation of the fluorescent ligand H{sub 3}L not only gives rise to a strong photoluminescence emission as expected, but more interestingly, that ligand originated characteristic band could be quenched selectively by nitrobenzene with a low detection limit, showing its potential as a highly sensitive and selective sensor for nitrobenzene. Based on an electron transfer quenching mechanism, the fluorescence sensing ability of 1 is also applicable for other electron-deficient nitroaromatic compounds with high selectivity and sensitivity, i.e., 1,4-dinitrobenzene, 1,3-dinitrobenzene, 2,4-dinitrotoluene, and 4-nitrotoluene, suggesting 1 a promising fluorescence sensor for detecting and recognizing the same kind of chemicals.

  13. In silico screening of metal–organic frameworks in separation applications

    SciTech Connect (OSTI)

    Krishna, Rajamani; van Baten, Jasper M.

    2011-05-03

    Porous materials such as metal–organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs) offer considerable potential for separating a variety of mixtures such as those relevant for CO₂ capture (CO₂/H₂, CO₂/CH₄, CO₂/N₂), CH₄/H₂, alkanes/alkenes, and hydrocarbon isomers. There are basically two different separation technologies that can be employed: (1) a pressure swing adsorption (PSA) unit with a fixed bed of adsorbent particles, and (2) a membrane device, wherein the mixture is allowed to permeate through a micro-porous crystalline layer. In view of the vast number of MOFs, and ZIFs that have been synthesized there is a need for a systematic screening of potential candidates for any given separation task. Also of importance is to investigate how MOFs and ZIFs stack up against the more traditional zeolites such as NaX and NaY with regard to their separation characteristics. This perspective highlights the potency of molecular simulations in determining the choice of the best MOF or ZIF for a given separation task. A variety of metrics that quantify the separation performance, such as adsorption selectivity, working capacity, diffusion selectivity, and membrane permeability, are determined from a combination of Configurational-Bias Monte Carlo (CBMC) and Molecular Dynamics (MD) simulations. The practical utility of the suggested screening methodology is demonstrated by comparison with available experimental data.

  14. Tunable electrical conductivity in oriented thin films of tetrathiafulvalene-based covalent organic framework

    SciTech Connect (OSTI)

    Cai, SL; Zhang, YB; Pun, AB; He, B; Yang, JH; Toma, FM; Sharp, ID; Yaghi, OM; Fan, J; Zheng, SR; Zhang, WG; Liu, Y

    2014-09-16

    Despite the high charge-carrier mobility in covalent organic frameworks (COFs), the low intrinsic conductivity and poor solution processability still impose a great challenge for their applications in flexible electronics. We report the growth of oriented thin films of a tetrathiafulvalene-based COF (TTF-COF) and its tunable doping. The porous structure of the crystalline TTF-COF thin film allows the diffusion of dopants such as I-2 and tetracyanoquinodimethane (TCNQ) for redox reactions, while the closely packed 2D grid sheets facilitate the cross-layer delocalization of thus-formed TTF radical cations to generate more conductive mixed-valence TTF species, as is verified by UV-vis-NIR and electron paramagnetic resonance spectra. Conductivity as high as 0.28 S m(-1) is observed for the doped COF thin films, which is three orders of magnitude higher than that of the pristine film and is among the highest for COF materials.

  15. Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal-Organic...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    MOFs with different open metal sites and ultra-large 1D channels, PCN-222 (Fe, Mn, Co, Ni, Cu, and Zn), have been assembled with eight-connected Zr6 clusters and redox-active...

  16. Biomimicry in metal-organic materials | Center for GasSeparationsRele...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Biomimicry in metal-organic materials Previous Next List Muwei Zhang, Zhi-Yuan Gu, Mathieu Bosch, Zachary Perry, Hong-Cai Zhou, Coordination Chemistry Reviews, (2014) DOI: 10.1016...

  17. Method for separating contaminants from solution employing an organic-stabilized metal-hydroxy gel

    DOE Patents [OSTI]

    Alexander, Donald H.

    1996-01-01

    Metals and organics are extracted from solution by co-precipitating them with a gel comprising aluminum hydroxide and a complexing agent such as EDTA. After the gel is processed to remove the metals and organics, it can be recycled for further use by dissolving it in a high-pH solution, leaving no secondary waste stream. A number of alternative complexing agents perform better than EDTA.

  18. Control organic-acid corrosion with these metals and alloys

    SciTech Connect (OSTI)

    Schillmoller, C.M.

    1997-02-01

    This article discusses materials selection for equipment used in the manufacture and storage of formic, acetic, and propionic acids. The author presents selected data and recommendations relating to higher-molecular-weight organic acids. In general, the corrosive action of organic acids decreases with increasing molecular weight. However, at high temperatures, the acids can dissociate, forming more aggressive ions which can cause much faster corrosion rates than might otherwise be expected. As a rule, stainless steels are attacked more violently by anhydrous organic acids than by organic acids which contain traces of water.

  19. A Reversible Crystallinity-Preserving Phase Transition in Metal...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Reversible Crystallinity-Preserving Phase Transition in Metal-Organic Frameworks: Discovery, Mechanistic Studies, and Potential Applications Previous Next List Liu, Dahuan; Liu,...

  20. A stepwise transition from microporosity to mesoporosity in metal...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    stepwise transition from microporosity to mesoporosity in metal-organic frameworks by thermal treatment Previous Next List Daqiang Yuan, Dan Zhao, Daren J. Timmons and Hong-Cai...

  1. Crystal Engineering on Superpolyhedral Building Blocks in Metal...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    on Superpolyhedral Building Blocks in Metal-Organic Frameworks Applied in Gas Adsorption. Acta Crystallogr., Sect. B: Struct. Sci., Cryst. Eng. Mater., 71, 613-618 (2015). DOI:...

  2. Metal-Containing Organic and Carbon Aerogels for Hydrogen Storage

    SciTech Connect (OSTI)

    Satcher, Jr., J H; Baumann, T F; Herberg, J L

    2005-01-10

    This document and the accompanying manuscript summarize the technical accomplishments of our one-year LDRD-ER effort. Hydrogen storage and hydrogen fuel cells are important components of the 2003 Hydrogen Fuel Initiative focused on the reduction of America's dependence on oil. To compete with oil as an energy source, however, one must be able to transport and utilize hydrogen at or above the target set by DOE (6 wt.% H{sub 2}) for the transportation sector. Other than liquid hydrogen, current technology falls well short of this DOE target. As a result, a variety of materials have recently been investigated to address this issue. Carbon nanostructures have received significant attention as hydrogen storage materials due to their low molecular weight, tunable microporosity and high specific surface areas. For example, the National Renewable Energy Laboratory (NREL) achieved 5 to 10 wt.% H{sub 2} storage using metal-doped carbon nanotubes. That study showed that the intimate mix of metal nanoparticles with graphitic carbon resulted in the unanticipated hydrogen adsorption at near ambient conditions. The focus of our LDRD effort was the investigation of metal-doped carbon aerogels (MDCAs) as hydrogen storage materials. In addition to their low mass densities, continuous porosities and high surface areas, these materials are promising candidates for hydrogen storage because MDCAs contain a nanometric mix of metal nanoparticles and graphitic nanostructures. For FY04, our goals were to: (1) prepare a variety of metal-doped CAs (where the metal is cobalt, nickel or iron) at different densities and carbonization temperatures, (2) characterize the microstructure of these materials and (3) initiate hydrogen adsorption/desorption studies to determine H2 storage properties of these materials. Since the start of this effort, we have successfully prepared and characterized Ni- and Co-doped carbon aerogels at different densities and carbonization temperatures. The bulk of this

  3. Surfactant biocatalyst for remediation of recalcitrant organics and heavy metals

    DOE Patents [OSTI]

    Brigmon, Robin L.; Story, Sandra; Altman, Denis J.; Berry, Christopher J.

    2011-05-03

    Novel strains of isolated and purified bacteria have been identified which have the ability to degrade petroleum hydrocarbons including a variety of PAHs. Several isolates also exhibit the ability to produce a biosurfactant. The combination of the biosurfactant-producing ability along with the ability to degrade PAHs enhances the efficiency with which PAHs may be degraded. Additionally, the biosurfactant also provides an additional ability to bind heavy metal ions for removal from a soil or aquatic environment.

  4. Surfactant biocatalyst for remediation of recalcitrant organics and heavy metals

    DOE Patents [OSTI]

    Brigmon, Robin L.; Story, Sandra; Altman, Denis J.; Berry, Christopher J.

    2011-03-15

    Novel strains of isolated and purified bacteria have been identified which have the ability to degrade petroleum hydrocarbons including a variety of PAHs. Several isolates also exhibit the ability to produce a biosurfactant. The combination of the biosurfactant-producing ability along with the ability to degrade PAHs enhances the efficiency with which PAHs may be degraded. Additionally, the biosurfactant also provides an additional ability to bind heavy metal ions for removal from a soil or aquatic environment.

  5. Surfactant biocatalyst for remediation of recalcitrant organics and heavy metals

    DOE Patents [OSTI]

    Brigmon, Robin L.; Story, Sandra; Altman; Denis J.; Berry, Christopher J.

    2011-03-29

    Novel strains of isolated and purified bacteria have been identified which have the ability to degrade petroleum hydrocarbons including a variety of PAHs. Several isolates also exhibit the ability to produce a biosurfactant. The combination of the biosurfactant-producing ability along with the ability to degrade PAHs enhances the efficiency with which PAHs may be degraded. Additionally, the biosurfactant also provides an additional ability to bind heavy metal ions for removal from a soil or aquatic environment.

  6. Surfactant biocatalyst for remediation of recalcitrant organics and heavy metals

    DOE Patents [OSTI]

    Brigmon, Robin L.; Story, Sandra; Altman, Denis; Berry, Christopher J.

    2009-01-06

    Novel strains of isolated and purified bacteria have been identified which have the ability to degrade petroleum hydrocarbons including a variety of PAHs. Several isolates also exhibit the ability to produce a biosurfactant. The combination of the biosurfactant-producing ability along with the ability to degrade PAHs enhances the efficiency with which PAHs may be degraded. Additionally, the biosurfactant also provides an additional ability to bind heavy metal ions for removal from a soil or aquatic environment.

  7. GTT Framework

    Broader source: Energy.gov [DOE]

    The GTT proposes a strategic framework that organizes these activities into three interrelated dimensions (informational, analytical, and physical), representative of the systems nature of the grid.

  8. Investigating the validity of the Knudsen prescription for diffusivities in a mesoporous covalent organic framework

    SciTech Connect (OSTI)

    Krishna, Rajamani; van Baten, Jasper M.

    2011-04-27

    Molecular dynamics (MD) simulations were performed to determine the self-diffusivity (Di,self) and the MaxwellStefan diffusivity (I) of hydrogen, argon, carbon dioxide, methane, ethane, propane, n-butane, n-pentane, and n-hexane in BTP-COF, which is a covalent organic framework (COF) that has one-dimensional 3.4-nm-sized channels. The MD simulations show that the zero-loading diffusivity (I(0)) is consistently lower, by up to a factor of 10, than the Knudsen diffusivity (Di,Kn) values. The ratio I(0)/Di,Kn is found to correlate with the isosteric heat of adsorption, which, in turn, is a reflection of the binding energy for adsorption on the pore walls: the stronger the binding energy, the lower the ratio I(0)/Di,Kn. The diffusion selectivity, which is defined by the ratio D1,self/D2,self for binary mixtures, was determined to be significantly different from the Knudsen selectivity (M2/M1)1/2, where MI is the molar mass of species i. For mixtures in which component 2 is more strongly adsorbed than component 1, the expression (D1,self/D2,self)/(M2/M1)1/2 has values in the range of 110; the departures from the Knudsen selectivity increased with increasing differences in adsorption strengths of the constituent species. The results of this study have implications in the modeling of diffusion within mesoporous structures, such as MCM-41 and SBA-15.

  9. Hybrid metal organic scintillator materials system and particle detector

    DOE Patents [OSTI]

    Bauer, Christina A.; Allendorf, Mark D.; Doty, F. Patrick; Simmons, Blake A.

    2011-07-26

    We describe the preparation and characterization of two zinc hybrid luminescent structures based on the flexible and emissive linker molecule, trans-(4-R,4'-R') stilbene, where R and R' are mono- or poly-coordinating groups, which retain their luminescence within these solid materials. For example, reaction of trans-4,4'-stilbenedicarboxylic acid and zinc nitrate in the solvent dimethylformamide (DMF) yielded a dense 2-D network featuring zinc in both octahedral and tetrahedral coordination environments connected by trans-stilbene links. Similar reaction in diethylformamide (DEF) at higher temperatures resulted in a porous, 3-D framework structure consisting of two interpenetrating cubic lattices, each featuring basic to zinc carboxylate vertices joined by trans-stilbene, analogous to the isoreticular MOF (IRMOF) series. We demonstrate that the optical properties of both embodiments correlate directly with the local ligand environments observed in the crystal structures. We further demonstrate that these materials produce high luminescent response to proton radiation and high radiation tolerance relative to prior scintillators. These features can be used to create sophisticated scintillating detection sensors.

  10. Composition and process for organic and metal contaminant fixation in soil

    DOE Patents [OSTI]

    Schwitzgebel, Klaus

    1994-02-08

    A method and compositions using a first ferrous iron containing solution with the iron concentration in excess of theoretical requirements to treat a contaminated site to reduce hexavalent chromium to trivalent chromium and coprecipitate trivalent chromium with other heavy metals and using a second solution of silicate containing a destabilizing salt to form a relatively impermeable gel in the contaminated site thereby fixing metals and organics to the extent that there should be no detectable ground water contamination.

  11. Substrate and environmental controls on microbial assimilation of soil organic carbon: a framework for Earth System Models

    SciTech Connect (OSTI)

    Xu, Xiaofeng; Schimel, Joshua; Thornton, Peter E; Song, Xia; Yuan, Fengming; Goswami, Santonu

    2014-01-01

    Microbial assimilation of soil organic carbon is one of the fundamental processes of global carbon cycling and it determines the magnitude of microbial biomass in soils. Mechanistic understanding of microbial assimilation of soil organic carbon and its controls is important for to improve Earth system models ability to simulate carbon-climate feedbacks. Although microbial assimilation of soil organic carbon is broadly considered to be an important parameter, it really comprises two separate physiological processes: one-time assimilation efficiency and time-dependent microbial maintenance energy. Representing of these two mechanisms is crucial to more accurately simulate carbon cycling in soils. In this study, a simple modeling framework was developed to evaluate the substrate and environmental controls on microbial assimilation of soil organic carbon using a new term: microbial annual active period (the length of microbes remaining active in one year). Substrate quality has a positive effect on microbial assimilation of soil organic carbon: higher substrate quality (lower C:N ratio) leads to higher ratio of microbial carbon to soil organic carbon and vice versa. Increases in microbial annual active period from zero stimulate microbial assimilation of soil organic carbon; however, when microbial annual active period is longer than an optimal threshold, increasing this period decreases microbial biomass. The simulated ratios of soil microbial biomass to soil organic carbon are reasonably consistent with a recently compiled global dataset at the biome-level. The modeling framework of microbial assimilation of soil organic carbon and its controls developed in this study offers an applicable ways to incorporate microbial contributions to the carbon cycling into Earth system models for simulating carbon-climate feedbacks and to explain global patterns of microbial biomass.

  12. A Physically Based Framework for Modelling the Organic Fractionation of Sea Spray Aerosol from Bubble Film Langmuir Equilibria

    SciTech Connect (OSTI)

    Burrows, Susannah M.; Ogunro, O.; Frossard, Amanda; Russell, Lynn M.; Rasch, Philip J.; Elliott, S.

    2014-12-19

    The presence of a large fraction of organic matter in primary sea spray aerosol (SSA) can strongly affect its cloud condensation nuclei activity and interactions with marine clouds. Global climate models require new parameterizations of the SSA composition in order to improve the representation of these processes. Existing proposals for such a parameterization use remotely-sensed chlorophyll-a concentrations as a proxy for the biogenic contribution to the aerosol. However, both observations and theoretical considerations suggest that existing relationships with chlorophyll-a, derived from observations at only a few locations, may not be representative for all ocean regions. We introduce a novel framework for parameterizing the fractionation of marine organic matter into SSA based on a competitive Langmuir adsorption equilibrium at bubble surfaces. Marine organic matter is partitioned into classes with differing molecular weights, surface excesses, and Langmuir adsorption parameters. The classes include a lipid-like mixture associated with labile dissolved organic carbon (DOC), a polysaccharide-like mixture associated primarily with semi-labile DOC, a protein-like mixture with concentrations intermediate between lipids and polysaccharides, a processed mixture associated with recalcitrant surface DOC, and a deep abyssal humic-like mixture. Box model calculations have been performed for several cases of organic adsorption to illustrate the underlying concepts. We then apply the framework to output from a global marine biogeochemistry model, by partitioning total dissolved organic carbon into several classes of macromolecule. Each class is represented by model compounds with physical and chemical properties based on existing laboratory data. This allows us to globally map the predicted organic mass fraction of the nascent submicron sea spray aerosol. Predicted relationships between chlorophyll-\\textit{a} and organic fraction are similar to existing empirical

  13. A stepwise transition from microporosity to mesoporosity in metal-organic frameworks by thermal treatment

    SciTech Connect (OSTI)

    Yuan, Daqiang; Zhao, Dan; Timmons, Daren J; Zhou, Hong-Cai

    2011-01-01

    A Cd MOF with twisted partially augmented the net was synthesized. Activation at increasing temperatures revealed an unprecedented stepwise transition from microporosity to mesoporosity. This thermal treatment may serve as an alternative approach for the preparation of mesoporous MOFs.

  14. CO2 Capture by Metal-Organic Frameworks with van der Waals Density...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    However, two specific vdW-DFs result in excellent agreement with experiments within a few kilojoules per mole, at a reduced computational cost compared to quantum chemistry or ...

  15. Experimental Evidence of Negative Linear Compressibility in the MIL-53 Metal-Organic Framework Family

    SciTech Connect (OSTI)

    Serra-Crespo, Pablo; Dikhtiarenko, Alla; Stavitski, Eli; Juan-Alcaniz, Jana; Kapeteijn, Freek; Coudert, Francois-Xavier; Gascon, Jorge

    2014-03-24

    Here, we report a series of powder X-ray diffraction experiments performed on the soft porous crystals MIL-53(Al) and NH2-MIL-53(Al) in a diamond anvil cell under different pressurization media. Systematic refinements of the obtained powder patterns demonstrate that these materials expand along a specific direction while undergoing total volume reduction under an increasing hydrostatic pressure. Our results confirm for the first time the negative linear compressibility behaviour of this family of materials, recently predicted from quantum chemical calculations.

  16. Experimental Evidence of Negative Linear Compressibility in the MIL-53 Metal-organic Framework Family

    SciTech Connect (OSTI)

    Serra-Crespo, Pablo; Dikhtiarenko, Alla; Stavitski, Eli; Juan-Alcaniz, Jana; Kapteijn, Freek; Coudert, Francois-Xavier; Gascon, Jorge

    2014-03-24

    Here we report a series of powder X-ray diffraction experiments performed on the soft porous crystals MIL-53(Al) and NH2-MIL-53(Al) in a diamond anvil cell under different pressurization media. Systematic refinements of the obtained powder patterns demonstrate that these materials expand along a specific direction while undergoing total volume reduction under an increasing hydrostatic pressure. Our results confirm for the first time the negative linear compressibility behaviour of this family of materials, recently predicted from quantum chemical calculations.

  17. Robust, Chiral, and Porous BINAP-Based Metal–Organic Frameworks...

    Office of Scientific and Technical Information (OSTI)

    (ANL), Argonne, IL (US) Sponsoring Org: NSF Country of Publication: United States Language: ENGLISH Word Cloud More Like This Full Text Journal Articles DOI: 10.1021jacs.5b09225

  18. Large-Pore Apertures in a Series of Metal-Organic Frameworks...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Terasaki, J. F. Stoddart, and O. M. Yaghi, Science 336 (6084), 1018 (2012) DOI: 10.1126science.1220131 Fig. 1 Abstract: We report a strategy to expand the pore aperture of...

  19. Novel metal-organic frameworks for efficient stationary sources via oxyfuel combustion

    SciTech Connect (OSTI)

    Nenoff, Tina M.; Sava Gallis, Dorina Florentina; Parkes, Marie Vernell; Greathouse, Jeffery A.; Rodriguez, Mark A.; Paap, Scott M; Williams, Timothy; Shaddix, Christopher R.

    2015-09-01

    Oxy-fuel combustion is a well-known approach to improve the heat transfer associated with stationary energy processes. Its overall penetration into industrial and power markets is constrained by the high cost of existing air separation technologies for generating oxygen. Cryogenic air separation is the most widely used technology for generating oxygen but is complex and expensive. Pressure swing adsorption is a competing technology that uses activated carbon, zeolites and polymer membranes for gas separations. However, it is expensive and limited to moderate purity O₂ . MOFs are cutting edge materials for gas separations at ambient pressure and room temperature, potentially revolutionizing the PSA process and providing dramatic process efficiency improvements through oxy-fuel combustion. This LDRD combined (1) MOF synthesis, (2) gas sorption testing, (3) MD simulations and crystallography of gas siting in pores for structure-property relationship, (4) combustion testing and (5) technoeconomic analysis to aid in real-world implementation.

  20. Computational study of hydrocarbon adsorption in metal-organic framework Ni2(dhtp)

    SciTech Connect (OSTI)

    Sun, Xiuquan; Wick, Collin D.; Thallapally, Praveen K.; McGrail, B. Peter; Dang, Liem X.

    2011-03-31

    Molecular dynamic simulations were carried out to study the sorption, structural properties, and diffusivities of n-hexane and cyclohexane adsorbed in Ni2(dhtp). The results indicated strong interactions between the alkanes and the host material. The free energy perturbation method was employed to investigate the adsorption free energies of methane, ethane, n-butane, n-hexane and cyclohexane. For linear alkanes, the free energy lowered as the length of the carbon chain increased. Also, the adsorption of n-hexane was preferred over cyclohexane, due to its ability to rearrange its structure to maximize contacts with the host. Furthermore, due to the large pore size of Ni2(dhtp), higher loadings of alkanes did not significantly affect the alkane structure, and enhanced the free energy of adsorption for subsequent alkanes being loaded. According to our studies, Ni2(dhtp) has a very promising potential for adsorption and storage of alkanes. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  1. Solid lithium electrolyte via addition of lithium salts to metal-organic frameworks

    DOE Patents [OSTI]

    Wiers, Brian M.; Balsara, Nitash P.; Long, Jeffrey R.

    2016-03-29

    Various embodiments of the invention disclose that the uptake of LiO.sup.iPr in Mg.sub.2(dobdc) (dobdc.sup.4-=1,4-dioxido-2,5-benzenedicarboxylate) followed by soaking in a typical electrolyte solution leads to a new solid lithium electrolyte Mg.sub.2(dobdc).0.35LiO.sup.iPr.0.25LiBF.sub.4.EC.DEC. Two-point ac impedance data show a pressed pellet of this material to have a conductivity of 3.1.times.10.sup.-4 S/cm at 300 K. In addition, the results from variable-temperature measurements reveal an activation energy of approximately 0.15 eV, while single-particle data suggest that intraparticle transport dominates conduction.

  2. Tuning the Moisture and Thermal Stability of Metal-Organic Frameworks...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    (MOFs) with different dialkoxy-substituents of formula Cu2(TPTC-OR) (TPTC-OR 2',5'-dialkyloxy-1,1':4',1''-terphenyl-3,3'',5,5''-tetracarboxylate, R Me, Et, nPr, nHex)...

  3. Anthraquinone with Tailored Structure for Nonaqueous Metal-Organic Redox Flow Battery

    SciTech Connect (OSTI)

    Wang, Wei; Xu, Wu; Cosimbescu, Lelia; Choi, Daiwon; Li, Liyu; Yang, Zhenguo

    2012-06-08

    A nonaqueous, hybrid metal-organic redox flow battery based on tailored anthraquinone structure is demonstrated to have an energy efficiency of {approx}82% and a specific discharge energy density similar to aqueous redox flow batteries, which is due to the significantly improved solubility of anthraquinone in supporting electrolytes.

  4. Surface functionalization of metal?organic polyhedron for homogeneous cyclopropanation catalysis

    SciTech Connect (OSTI)

    Lu, Weigang; Yuan, Daqiang; Yakovenko, Andrey; Zhou, Hong-Cai

    2012-03-13

    A super-paddlewheel (comprised of two paddlewheels) metal-organic polyhedron (MOP) containing surface hydroxyl groups was synthesized and characterized. Condensation reactions with linear alkyl anhydrides lead to new MOPs with enhanced solubility. As a result, the surface-modified MOP 4 was demonstrated as a homogeneous Lewis-acid catalyst.

  5. Metal-organic scintillator crystals for X-ray, gamma ray, and neutron detection

    DOE Patents [OSTI]

    Boatner, Lynn A (Oak Ridge, TN); Kolopus, James A. (Clinton, TN); Neal, John S (Knoxville, TN); Ramey, Joanne Oxendine (Knoxville, TN); Wisniewski, Dariusz J (Torun, PL)

    2012-01-03

    New metal-organic materials are useful as scintillators and have the chemical formula LX.sub.3(CH.sub.3OH).sub.4 where L is Y, Sc, or a lanthanide element, and X is a halogen element. An example of the scintillator materials is CeCl.sub.3(CH.sub.3OH).sub.4.

  6. White organic light-emitting diodes with 4 nm metal electrode

    SciTech Connect (OSTI)

    Lenk, Simone; Schwab, Tobias; Schubert, Sylvio; Müller-Meskamp, Lars; Leo, Karl; Reineke, Sebastian; Gather, Malte C.

    2015-10-19

    We investigate metal layers with a thickness of only a few nanometers as anode replacement for indium tin oxide (ITO) in white organic light-emitting diodes (OLEDs). The ultrathin metal electrodes prove to be an excellent alternative that can, with regard to the angular dependence and efficiency of the OLED devices, outperform the ITO reference. Furthermore, unlike ITO, the thin composite metal electrodes are readily compatible with demanding architectures (e.g., top-emission or transparent OLEDs, device unit stacking, etc.) and flexible substrates. Here, we compare the sheet resistance of both types of electrodes on polyethylene terephthalate for different bending radii. The electrical performance of ITO breaks down at a radius of 10 mm, while the metal electrode remains intact even at radii smaller than 1 mm.

  7. Strong and Reversible Binding of Carbon Dioxide in a Green Metal...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Strong and Reversible Binding of Carbon Dioxide in a Green Metal-Organic Framework Previous Next List Jeremiah J. Gassensmith, Hiroyasu Furukawa, Ronald A. Smaldone, Ross S. ...

  8. Metal-doped organic foam and method of making same. [Patent application

    DOE Patents [OSTI]

    Rinde, J.A.

    Organic foams having a low density and very small cell size and method for producing same in either a metal-loaded or unloaded (nonmetal loaded) form are described. Metal-doped foams are produced by soaking a polymer gel in an aqueous solution of desired metal salt, soaking the gel successively in a solvent series of decreasing polarity to remove water from the gel and replace it with a solvent of lower polarity with each successive solvent in the series being miscible with the solvents on each side and being saturated with the desired metal salt, and removing the last of the solvents from the gel to produce the desired metal-doped foam having desired density cell size, and metal loading. The unloaded or metal-doped foams can be utilized in a variety of applications requiring low density, small cell size foam. For example, rubidium-doped foam made in accordance with the invention has utility in special applications, such as in x-ray lasers.

  9. Rigidifying Fluorescent Linkers by Metal–Organic Framework Formation for Fluorescence Blue Shift and Quantum Yield Enhancement

    SciTech Connect (OSTI)

    Wei, Zhangwen; Gu, Zhi-Yuan; Arvapally, Ravi K.; Chen, Ying-Pin; Ivy, Joshua F.; Yakovenko, Andrey A.; Feng, Dawei; Omary, Mohammad A.; Zhou, Hong-Cai

    2014-06-11

    We demonstrate that rigidifying the structure of fluorescent linkers by structurally constraining them in metal–organic frameworks (MOFs) to control their conformation effectively tunes the fluorescence energy and enhances the quantum yield. Thus, a new tetraphenylethylene-based zirconium MOF exhibits a deep-blue fluorescent emission at 470 nm with a unity quantum yield (99.9 ± 0.5%) under Ar, representing ca. 3600 cm⁻¹ blue shift and doubled radiative decay efficiency vs the linker precursor. An anomalous increase in the fluorescence lifetime and relative intensity takes place upon heating the solid MOF from cryogenic to ambient temperatures. The origin of these unusual photoluminescence properties is attributed to twisted linker conformation, intramolecular hindrance, and framework rigidity.

  10. A Framework for Organizing Current and Future Electric Utility Regulatory and Business Models

    Broader source: Energy.gov [DOE]

    In this report, we will present a descriptive and organizational framework for incremental and fundamental changes to regulatory and utility business models in the context of clean energy public policy goals. We will also discuss the regulated utility's role in providing value-added services that relate to distributed energy resources, identify the "openness" of customer information and utility networks necessary to facilitate change, and discuss the relative risks, and the shifting of risks, for utilities and customers.

  11. Life cycle cost study for coated conductor manufacture by metal organic chemical vapor deposition

    SciTech Connect (OSTI)

    Chapman, J.N.

    1999-07-13

    The purpose of this report is to calculate the cost of producing high temperature superconducting wire by the Metal Organic Chemical Vapor Deposition (MOCVD) process. The technology status is reviewed from the literature and a plant conceptual design is assumed for the cost calculation. The critical issues discussed are the high cost of the metal organic precursors, the material utilization efficiency and the capability of the final product as measured by the critical current density achieved. Capital, operating and material costs are estimated and summed as the basis for calculating the cost per unit length of wire. Sensitivity analyses of key assumptions are examined to determine their effects on the final wire cost. Additionally, the cost of wire on the basis of cost per kiloampere per meter is calculated for operation at lower temperatures than the liquid nitrogen boiling temperature. It is concluded that this process should not be ruled out on the basis of high cost of precursors alone.

  12. Organic-Inorganic Complexes Containing a Luminescent Rare Earth-Metal

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Nanocluster and an Antenna Ligand, Luminescent Articles, and Methods of Making Luminescent Articles - Energy Innovation Portal Solar Photovoltaic Solar Photovoltaic Energy Storage Energy Storage Building Energy Efficiency Building Energy Efficiency Advanced Materials Advanced Materials Find More Like This Return to Search Organic-Inorganic Complexes Containing a Luminescent Rare Earth-Metal Nanocluster and an Antenna Ligand, Luminescent Articles, and Methods of Making Luminescent Articles

  13. Structure-Assisted Functional Anchor Implantation in Robust Metal–Organic Frameworks with Ultralarge Pores

    SciTech Connect (OSTI)

    Park, Jihye; Feng, Dawei; Zhou, Hong-Cai

    2015-02-04

    A facile functionalization assisted by the structural attributes of PCN-333 has been studied while maintaining the integrity of the parent MOF including ultralarge pores, chemical robustness, and crystallinity. Herein we thoroughly analyzed ligand exchange phenomena in PCN-333 and demonstrate that the extent of exchange can be tailored by varying the exchange conditions as potential applications may require. Through this method a variety of functional groups are incorporated into PCN-333. To further show the capabilities of this system introduction of a BODIPY fluorophore as a secondary functionality was performed to the functionalized framework via a click reaction. We anticipate the PCN-333 with functional anchor can serve as a stable platform for further chemistry to be explored in future applications.

  14. Structural and degradation studies of a biocompatible Zn-L-tartrate metal–organic framework

    SciTech Connect (OSTI)

    Palǒić, Ana; Puškarić, Andreas; Mazaj, Matjaž; Žunkoviǒ, Emanuela; Logar, Nataša Zabukovec; Bronić, Josip

    2015-05-15

    New anhydrous Zn-L-tratrate was synthesized under hydrothermal conditions. Crystal structure which was solved by powder X-ray diffraction data from monoclinic unit cell (I{sub 2}, a=11.7557(1), b=9.0319(1), c=5.0750(1), β=91.920(1)) consists of the three-dimensional framework where each Zn atom coordinates four tartrate ligands in distorted octahedral geometry. Due to its biocompatible components, the degradation of material was studied in aqueous media under different pH values (pH=1–7) and in the simulated body fluid (pH=7.4) performed by the measurement of the released Zn{sup 2+} concentrations at thermostatic conditions (37 °C). The results showed that under acidic conditions approximately 60% of Zn{sup 2+} is released from the investigated material after 6 h of degradation process. With the increase of the solution’s pH, the rate of degradation gradually decreases. XRD and SEM analyses indicate that in aqueous media the compound slowly disintegrates and does not undergo hydrolysis process regardless of pH. Biocompatibility of the compound and its controllable rate of degradation even in acid conditions open its potential use in the fields of bio-applications. - Graphical abstract: The degradation kinetics of Zn-L-tar MOF material in aqueous media at different pH conditions. - Highlights: • Anhydrous chiral Zn-L-tratrate was synthesized under hydrothermal conditions. • 3-D framework consists of Zn atoms, each chelating four tartrate ligands. • Degradation of material was studied in aqueous media at different pH values. • The compound disintegrates in controllable manner in aqueous solutions. • The rate compound degradation is increasing with increased acidity of solution.

  15. Pore-Controlled Formation of 0D Metal Complexes in Anionic 3D...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Pore-Controlled Formation of 0D Metal Complexes in Anionic 3D Metal-Organic Frameworks Previous Next List Muwei Zhang, Mathieu Boscha and Hong-Cai Zhou, Cryst. Eng. Comm, 17,...

  16. Pore-controlled formation of 0D metal complexes in anionic 3D...

    Office of Scientific and Technical Information (OSTI)

    Title: Pore-controlled formation of 0D metal complexes in anionic 3D metal-organic frameworks Authors: Zhang, Muwei ; Bosch, Mathieu ; Zhou, Hong-Cai Publication Date: 2015-01-01 ...

  17. Metal-organic molecular device for non-volatile memory storage

    SciTech Connect (OSTI)

    Radha, B., E-mail: radha.boya@manchester.ac.uk, E-mail: kulkarni@jncasr.ac.in; Sagade, Abhay A.; Kulkarni, G. U., E-mail: radha.boya@manchester.ac.uk, E-mail: kulkarni@jncasr.ac.in [Chemistry and Physics of Materials Unit and DST Unit on Nanoscience, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur P.O., Bangalore 560064 (India)

    2014-08-25

    Non-volatile memory devices have been of immense research interest for their use in active memory storage in powered off-state of electronic chips. In literature, various molecules and metal compounds have been investigated in this regard. Molecular memory devices are particularly attractive as they offer the ease of storing multiple memory states in a unique way and also represent ubiquitous choice for miniaturized devices. However, molecules are fragile and thus the device breakdown at nominal voltages during repeated cycles hinders their practical applicability. Here, in this report, a synergetic combination of an organic molecule and an inorganic metal, i.e., a metal-organic complex, namely, palladium hexadecylthiolate is investigated for memory device characteristics. Palladium hexadecylthiolate following partial thermolysis is converted to a molecular nanocomposite of Pd(II), Pd(0), and long chain hydrocarbons, which is shown to exhibit non-volatile memory characteristics with exceptional stability and retention. The devices are all solution-processed and the memory action stems from filament formation across the pre-formed cracks in the nanocomposite film.

  18. Stabilization of Rocky Flats combustible residues contaminated with plutonium metal and organic solvents

    SciTech Connect (OSTI)

    Bowen, S.M.; Cisneros, M.R.; Jacobson, L.L.; Schroeder, N.C.; Ames, R.L.

    1998-09-30

    This report describes tests on a proposed flowsheet designed to stabilize combustible residues that were generated at the Rocky Flats Environmental Technology Site (RFETS) during the machining of plutonium metal. Combustible residues are essentially laboratory trash contaminated with halogenated organic solvents and plutonium metal. The proposed flowsheet, designed by RFETS, follows a glovebox procedure that includes (1) the sorting and shredding of materials, (2) a low temperature thermal desorption of solvents from the combustible materials, (3) an oxidation of plutonium metal with steam, and (4) packaging of the stabilized residues. The role of Los Alamos National Laboratory (LANL) in this study was to determine parameters for the low temperature thermal desorption and steam oxidation steps. Thermal desorption of carbon tetrachloride (CCl{sub 4}) was examined using a heated air stream on a Rocky Flats combustible residue surrogate contaminated with CCl{sub 4}. Three types of plutonium metal were oxidized with steam in a LANL glovebox to determine the effectiveness of this procedure for residue stabilization. The results from these LANL experiments are used to recommend parameters for the proposed RFETS stabilization flowsheet.

  19. A nanoporous 3D zinc(II) metal–organic framework for selective absorption of benzaldehyde and formaldehyde

    SciTech Connect (OSTI)

    Moradpour, Tahereh; Abbasi, Alireza; Van Hecke, Kristof

    2015-08-15

    A new 3D nanoporous metal–organic framework (MOF), [[Zn{sub 4}O(C{sub 24}H{sub 15}N{sub 6}O{sub 6}){sub 2}(H{sub 2}O){sub 2}]·6H{sub 2}O·DMF]{sub n} (1) based on 4,4′,4″-s-triazine-1,3,5-triyltri-p-aminobenzoate (TATAB) ligand was solvothermally synthesized and characterized by single–crystal X-ray diffraction, Powder X-ray diffraction (PXRD), infrared spectroscopy (IR) and Brunauer–Emmett–Teller (BET) analyses. X-ray single crystal diffraction analysis reveals that 1 exhibits a 3D network with new kvh1 topology. Semi-empirical (AM1) calculations were carried out to obtain stable conformers for TATAB ligand. In addition, the absorption of two typical aldehydes (benzaldehyde and formaldehyde) in the presence of 1 was investigated and the effect of the aldehyde concentration, exposure time and temperature was studied. It was found that compound 1 has a potential for the absorption of aldehydes under mild conditions. - Graphical abstract: Absorption of two typical aldehydes (formaldehyde and benzaldehyde) by solvothermally synthesized of a 3D nano-porous MOF based on TATAB tricarboxylate ligand and Zn (NO{sub 3}){sub 2}·6H{sub 2}O. - Highlights: • We present a 3D Zn(II)-MOF with TATAB linker by solvothermal method. • The framework possesses a new kvh1 topology. • The framework displays formaldehyde and benzaldehyde absorption property. • Conformational analysis was performed to determine the stable linker geometry.

  20. The role of atropisomers on the photo-reactivity and fatigue of diarylethene-based metal–organic frameworks

    SciTech Connect (OSTI)

    Walton, Ian M.; Cox, Jordan M.; Benson, Cassidy A.; Patel, Dinesh G.; Chen, Yu-Sheng; Benedict, Jason B.

    2016-01-01

    Photo-responsive metal–organic frameworks (MOFs) are one example of light controlled smart materials for use in advanced sensors, data storage, actuators and molecular switches. Herein we show the design, synthesis and characterization of a photo-responsive linker that is subsequently reacted to yield MOF single crystals. The photo-responsive properties of the resulting UBMOF-2 arise from the photo-induced cyclization of the diarylethene moiety designed into the linker. Computational modeling to assess the relative energies of linker atropisomers reveals a large energetic barrier preventing facile interconversion between key species. The role of this barrier on the observed photo-induced fatigue provides useful insight into the development of advanced photo-responsive nanoporous materials.

  1. Method of making AlInSb by metal-organic chemical vapor deposition

    DOE Patents [OSTI]

    Biefeld, Robert M. (Albuquerque, NM); Allerman, Andrew A. (Albuquerque, NM); Baucom, Kevin C. (Albuquerque, NM)

    2000-01-01

    A method for producing aluminum-indium-antimony materials by metal-organic chemical vapor deposition (MOCVD). This invention provides a method of producing Al.sub.X In.sub.1-x Sb crystalline materials by MOCVD wherein an Al source material, an In source material and an Sb source material are supplied as a gas to a heated substrate in a chamber, said Al source material, In source material, and Sb source material decomposing at least partially below 525.degree. C. to produce Al.sub.x In.sub.1-x Sb crystalline materials wherein x is greater than 0.002 and less than one.

  2. A modular molecular framework for utility in small-molecule solution-processed organic photovoltaic devices

    SciTech Connect (OSTI)

    Welch, Gregory C; Perez, Louis A.; Hoven, Corey V.; Zhang, Yuan; Dang, Xuan-Dung; Sharenko, Alexander; Toney, Michael F.; Kramer, Edward J.; Nguyen, Thuc-Quyen; Bazan, Guillermo C.

    2011-01-01

    We report on the design, synthesis and characterization of light harvesting small molecules for use in solution-processed small molecule bulk heterojunction (SM-BHJ) solar cell devices. These molecular materials are based upon an acceptor/donor/acceptor (A/D/A) core with donor endcapping units. Utilization of a dithieno(3,2-b;2',3'-d)silole (DTS) donor and pyridal[2,1,3]thiadiazole (PT) acceptor leads to strong charge transfer characteristics, resulting in broad optical absorption spectra extending well beyond 700 nm. SM-BHJ solar cell devices fabricated with the specific example 5,5'-bis{7-(4-(5-hexylthiophen-2-yl)thiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine}-3,3'-di-2-ethylhexylsilylene-2,2'-bithiophene (6) as the donor and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) as the acceptor component showed short circuit currents above -10 mA cm-2 and power conversion efficiencies (PCEs) over 3%. Thermal processing is a critical factor in obtaining favorable active layer morphologies and high PCE values. A combination of UV-visible spectroscopy, conductive and photo-conductive atomic force microscopies, dynamic secondary mass ion spectrometry (DSIMS), and grazing incident wide angle X-ray scattering (GIWAXS) experiments were carried out to characterize how thermal treatment influences the active layer structure and organization.

  3. Preparation of functionalized zeolitic frameworks

    DOE Patents [OSTI]

    Yaghi, Omar M; Furukawa, Hiroyasu; Wang, Bo

    2013-07-09

    The disclosure provides zeolitic frameworks for gas separation, gas storage, catalysis and sensors. More particularly the disclosure provides zeolitic frameworks (ZIFs). The ZIF of the disclosure comprises any number of transition metals or a homogenous transition metal composition.

  4. Preparation of functionalized zeolitic frameworks

    DOE Patents [OSTI]

    Yaghi, Omar M.; Hayashi, Hideki; Banerjee, Rahul; Park, Kyo Sung; Wang, Bo; Cote, Adrien P.

    2014-08-19

    The disclosure provides zeolitic frameworks for gas separation, gas storage, catalysis and sensors. More particularly the disclosure provides zeolitic frameworks (ZIFs). The ZIF of the disclosure comprises any number of transition metals or a homogenous transition metal composition.

  5. Preparation of functionalized zeolitic frameworks

    DOE Patents [OSTI]

    Yaghi, Omar M; Hayashi, Hideki; Banerjee, Rahul; Park, Kyo Sung; Wang, Bo; Cote, Adrien P

    2012-11-20

    The disclosure provides zeolitic frameworks for gas separation, gas storage, catalysis and sensors. More particularly the disclosure provides zeolitic frameworks (ZIFs). The ZIF of the disclosure comprises any number of transition metals or a homogenous transition metal composition.

  6. A high surface area Zr(IV)-based metal–organic framework showing stepwise gas adsorption and selective dye uptake

    SciTech Connect (OSTI)

    Lv, Xiu-Liang; Tong, Minman; Huang, Hongliang; Wang, Bin; Gan, Lei; Yang, Qingyuan; Zhong, Chongli; Li, Jian-Rong

    2015-03-15

    Exploitation of new metal–organic framework (MOF) materials with high surface areas has been attracting great attention in related research communities due to their broad potential applications. In this work, a new Zr(IV)-based MOF, [Zr{sub 6}O{sub 4}(OH){sub 4}(eddb){sub 6}] (BUT-30, H{sub 2}eddb=4,4′-(ethyne-1,2-diyl)dibenzoic acid) has been solvothermally synthesized, characterized, and explored for gases and dyes adsorptions. Single-crystal X-ray diffraction analysis demonstrates a three-dimensional cubic framework structure of this MOF, in which each Zr{sub 6}O{sub 4}(OH){sub 4} building unit is linked by 12 linear eddb ligands. BUT-30 has been found stable up to 400 °C and has a Brunauer–Emmett–Teller (BET) surface area as high as 3940.6 m{sup 2} g{sup −1} (based on the N{sub 2} adsorption at 77 K) and total pore volume of 1.55 cm{sup 3} g{sup −1}. It is more interesting that this MOF exhibits stepwise adsorption behaviors for Ar, N{sub 2}, and CO{sub 2} at low temperatures, and selective uptakes towards different ionic dyes. - Graphical abstract: A new Zr(IV)-based MOF with high surface area has been synthesized and structurally characterized, which shows stepwise gas adsorption at low temperature and selective dye uptake from solution. - Highlights: • A new Zr-based MOF was synthesized and structurally characterized. • This MOF shows a higher surface area compared with its analogous UiO-67 and 68. • This MOF shows a rare stepwise adsorption towards light gases at low temperature. • This MOF performs selective uptakes towards cationic dyes over anionic ones. • Using triple-bond spacer is confirmed feasible in enhancing MOF surface areas.

  7. Development of HUMASORB{trademark}, a lignite derived humic acid for removal of metals and organic contaminants from groundwater

    SciTech Connect (OSTI)

    Sanjay, H.G.; Srivastave, K.C.; Walia, D.S.

    1995-10-01

    Heavy metal and organic contamination of surface and groundwater systems is a major environmental concern. The contamination is primarily due to improperly disposed industrial wastes. The presence of toxic heavy metal ions, volatile organic compounds (VOCs) and pesticides in water is of great concern and could affect the safety of drinking water. Decontamination of surface and groundwater can be achieved using a broad spectrum of treatment options such as precipitation, ion-exchange, microbial digestion, membrane separation, activated carbon adsorption, etc. The state of the art technologies for treatment of contaminated water however, can in one pass remediate only one class of contaminants, i.e., either VOCs (activated carbon) or heavy metals (ion exchange). This would require the use of at a minimum, two different stepwise processes to remediate a site. The groundwater contamination at different Department of Energy (DOE) sites (e.g., Hanford) is due to the presence of both VOCs and heavy metals. The two-step approach increases the cost of remediation. To overcome the sequential treatment of contaminated streams to remove both organics and metals, a novel material having properties to remove both classes of contaminants in one step is being developed as part of this project.The objective of this project is to develop a lignite-derived adsorbent, Humasorb{sup TM} to remove heavy metals and organics from ground water and surface water streams.

  8. High mobility single-crystalline-like GaAs thin films on inexpensive flexible metal substrates by metal-organic chemical vapor deposition

    SciTech Connect (OSTI)

    Dutta, P. Rathi, M.; Gao, Y.; Yao, Y.; Selvamanickam, V.; Zheng, N.; Ahrenkiel, P.; Martinez, J.

    2014-09-01

    We demonstrate heteroepitaxial growth of single-crystalline-like n and p-type doped GaAs thin films on inexpensive, flexible, and light-weight metal foils by metal-organic chemical vapor deposition. Single-crystalline-like Ge thin film on biaxially textured templates made by ion beam assisted deposition on metal foil served as the epitaxy enabling substrate for GaAs growth. The GaAs films exhibited strong (004) preferred orientation, sharp in-plane texture, low grain misorientation, strong photoluminescence, and a defect density of ?10{sup 7?}cm{sup ?2}. Furthermore, the GaAs films exhibited hole and electron mobilities as high as 66 and 300?cm{sup 2}/V-s, respectively. High mobility single-crystalline-like GaAs thin films on inexpensive metal substrates can pave the path for roll-to-roll manufacturing of flexible III-V solar cells for the mainstream photovoltaics market.

  9. Introduction of Functionality, Selection of Topology, and Enhancement of Gas Adsorption in Multivariate Metal–Organic Framework-177

    SciTech Connect (OSTI)

    Zhang, Yue-Biao; Furukawa, Hiroyasu; Ko, Nakeun; Nie, Weixuan; Park, Hye Jeong; Okajima, Satoshi; Cordova, Kyle E.; Deng, Hexiang; Kim, Jaheon; Yaghi, Omar M.

    2015-02-25

    Metal–organic framework-177 (MOF-177) is one of the most porous materials whose structure is composed of octahedral Zn4O(-COO)6 and triangular 1,3,5-benzenetribenzoate (BTB) units to make a three-dimensional extended network based on the qom topology. This topology violates a long-standing thesis where highly symmetric building units are expected to yield highly symmetric networks. In the case of octahedron and triangle combinations, MOFs based on pyrite (pyr) and rutile (rtl) nets were expected instead of qom. In this study, we have made 24 MOF-177 structures with different functional groups on the triangular BTB linker, having one or more functionalities. We find that the position of the functional groups on the BTB unit allows the selection for a specific net (qom, pyr, and rtl), and that mixing of functionalities (-H, -NH2, and -C4H4) is an important strategy for the incorporation of a specific functionality (-NO2) into MOF-177 where otherwise incorporation of such functionality would be difficult. Such mixing of functionalities to make multivariate MOF-177 structures leads to enhancement of hydrogen uptake by 25%.

  10. The structure-directed effect of Al-based metal–organic frameworks on fabrication of alumina by thermal treatment

    SciTech Connect (OSTI)

    Liu, Dandan; Dai, Fangna; Tang, Zhe; Liu, Yunqi; Liu, Chenguang

    2015-05-15

    Highlights: • We use Al-MOFs as precursor in the fabrication process of mesoporous alumina by thermal treatment. • The obtained mesoporous alumina has dual pore system and five-fold aluminum. • The aluminum building units in the precursor show structure-directed effect on the formation of alumina. - Abstract: In this work, the block-shaped Al-based metal–organic frameworks (Al-MOFs) MIL-53 have been synthesized by hydrothermal method. To detect the correlation between the structure of Al-MOFs and the formation of alumina, the ligands are eliminated by thermal treatment. MIL-53 and the calcination products were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), transmission electron microscopy (TEM), nitrogen adsorption–desorption and solid-state {sup 27}Al nuclear magnetic resonance ({sup 27}Al NMR). It was found that after calcination, the block-shaped Al-MOFs precursor turns into high-crystallinity mesoporous alumina nanosheets, and the thermal treatment product γ-alumina possesses a dual pore system and a large surface area (146 m{sup 2}/g), with five-fold aluminum. During the thermal treatment process, the structure of MIL-53 and its secondary building units have structure-directed effect in the formation of alumina.

  11. DNP-enhanced ultrawideline solid-state NMR spectroscopy: Studies of platinum in metal–organic frameworks

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Kobayashi, Takeshi; Perras, Frederic A.; Goh, Tian Wei; Metz, Tanner L.; Huang, Wenyu; Pruski, Marek

    2016-06-06

    Ultrawideline dynamic nuclear polarization (DNP)-enhanced 195Pt solid-state NMR (SSNMR) spectroscopy and theoretical calculations are used to determine the coordination of atomic Pt species supported within the pores of metal–organic frameworks (MOFs). The 195Pt SSNMR spectra, with breadths reaching 10,000 ppm, were obtained by combining DNP with broadbanded cross-polarization and CPMG acquisition. Although the DNP enhancements in static samples are lower than those typically observed under magic-angle spinning conditions, the presented measurements would be very challenging using the conventional SSNMR methods. The DNP-enhanced ultrawideline NMR spectra served to separate signals from cis- and trans-coordinated atomic Pt2+ species supported on the UiO-66-NH2more » MOF. Here, the data revealed a dominance of kinetic effects in the formation of Pt2+ complexes and the thermodynamic effects in their reduction to nanoparticles. A single cis-coordinated Pt2+ complex was confirmed in MOF-253.« less

  12. Efficient alkene epoxidation catalyzed by molybdenyl acetylacetonate supported on aminated UiO-66 metal−organic framework

    SciTech Connect (OSTI)

    Kardanpour, Reihaneh; Tangestaninejad, Shahram; Mirkhani, Valiollah; Moghadam, Majid; Mohammadpoor-Baltork, Iraj; Zadehahmadi, Farnaz

    2015-03-15

    Metal–organic frameworks (MOFs) containing Mo Schiff base complexes were prepared by post-synthesis method and applied as efficient catalysts in the epoxidation of alkenes with tert-BuOOH. In this manner, UiO-66-NH{sub 2} (UiO=University of Oslo) MOF was reacted with salicylaldehyde and thiophene-2-carbaldehyde to produce bidentate Schiff bases. Then, the Schiff base ligands were used for immobilization of molybdenyl acetylacetonate. These new catalysts were characterized by FT-IR, UV–vis spectroscopic techniques, X-ray diffraction (XRD), BET, inductively coupled plasma atomic emission spectroscopy (ICP-AES) and field emission scanning electron microscopy (FE-SEM). These catalytic systems showed excellent activity in the epoxidation of alkenes such as cyclic and linear ones with tert-butyl hydroperoxide (TBHP) in 1,2-dichloroethane, and reused several times without any appreciable loss of their activity. - Graphical abstract: Efficient alkene epoxidation with TBHP catalyzed by heterogeneous and reusable molybdenum base catalysts is reported. - Highlights: • UiO-66-NH{sub 2} was modified with salicylaldehyde and thiophene-2-carbaldehyde. • The Schiff base groups were used for immobilization of MoO{sub 2}(acac){sub 2}. • The heterogeneous catalysts were prepared. • The prepared catalysts were used for epoxidation of alkenes. • Compared to other catalyst, our catalysts were more efficient and forceful.

  13. Interplay of confinement and surface energetics in the interaction of water with a metal–organic framework

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Wu, Di; Guo, Xiaofeng; Sun, Hui; Navrotsky, Alexandra

    2016-03-24

    Here, the enthalpy of water adsorption (Δh) on the metal–organic framework (MOF) HKUST-1 has been determined directly by calorimetry. The most exothermic value of Δh [–119.4 ± 0.5 kJ/(mol of water)] occurs at zero coverage and perhaps represents water confinement in the smallest (4-Å) cages. An intermediate Δh value of –50.2 ± 1.8 kJ/(mol of water) at higher loading probably corresponds to the binding of water on the available Cu nodes and subsequent filling of the largest (11-Å) pores. The weakest interactions take place in the medium (10-Å) cages, showing weak inclusion of water clusters in a limited hydrophobic environment.more » By combining ethanol adsorption calorimetry, mathematical analysis of the slope of the water adsorption isotherm, and the differential enthalpy of water adsorption curve, we are able not only to develop an approach to separate energetically multistage guest–host interactions in complex MOF architectures but also to distinguish a sequence of interactions with very similar energetic effects.« less

  14. Fully transparent organic transistors with junction-free metallic network electrodes

    SciTech Connect (OSTI)

    Pei, Ke; Wang, Zongrong; Ren, Xiaochen; Zhang, Zhichao; Peng, Boyu; Chan, Paddy K. L.

    2015-07-20

    We utilize highly transparent, junction-free metal network electrodes to fabricate fully transparent organic field effect transistors (OFETs). The patterned transparent Ag networks are developed by polymer crack template with adjustable line width and density. Sheet resistance of the network is 6.8 Ω/sq and optical transparency in the whole visible range is higher than 80%. The bottom contact OFETs with DNTT active layer and parylene-C dielectric insulator show a maximum field-effect mobility of 0.13 cm{sup 2}/V s (average mobility is 0.12 cm{sup 2}/V s) and on/off ratio is higher than 10{sup 7}. The current OFETs show great potential for applications in the next generation of transparent and flexible electronics.

  15. metals Fischer, S.H.; Grubelich, M.C. 37 INORGANIC, ORGANIC,...

    Office of Scientific and Technical Information (OSTI)

    IGNITION; MIXTURES; PRODUCTION; REACTION HEAT; SPECIFIC HEAT; STABILITY Thermite (metal oxide) mixtures, intermetallic reactants, and metal fuels have long been used in...

  16. Redox chemistry and metal-insulator transitions intertwined in...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    The ferrous salt of 2,5-dihydroxy-terephthalic acid, a metal-organic framework of the MOF74 family, can selectively adsorb oxygen in a manner that defies the classical picture: ...

  17. Mechanistic Studies of Charge Injection from Metallic Electrodes into Organic Semiconductors Mediated by Ionic Functionalities: Final Report

    SciTech Connect (OSTI)

    Nguyen, Thuc-Quyen; Bazan, Guillermo; Mikhailovsky, Alexander

    2014-04-15

    Metal-organic semiconductor interfaces are important because of their ubiquitous role in determining the performance of modern electronics such as organic light emitting diodes (OLEDs), fuel cells, batteries, field effect transistors (FETs), and organic solar cells. Interfaces between metal electrodes required for external wiring to the device and underlying organic structures directly affect the charge carrier injection/collection efficiency in organic-based electronic devices primarily due to the mismatch between energy levels in the metal and organic semiconductor. Environmentally stable and cost-effective electrode materials, such as aluminum and gold typically exhibit high potential barriers for charge carriers injection into organic devices leading to increased operational voltages in OLEDs and FETs and reduced charge extraction in photovoltaic devices. This leads to increased power consumption by the device, reduced overall efficiency, and decreased operational lifetime. These factors represent a significant obstacle for development of next generation of cheap and energy-efficient components based on organic semiconductors. It has been noticed that introduction of organic materials with conjugated backbone and ionic pendant groups known as conjugated poly- and oligoelectrolytes (CPEs and COEs), enables one to reduce the potential barriers at the metal-organic interface and achieve more efficient operation of a device, however exact mechanisms of the phenomenon have not been understood. The goal of this project was to delineate the function of organic semiconductors with ionic groups as electron injection layers. The research incorporated a multidisciplinary approach that encompassed the creation of new materials, novel processing techniques, examination of fundamental electronic properties and the incorporation of the resulting knowledgebase into development of novel organic electronic devices with increased efficiency, environmental stability, and reduced

  18. Unipolar resistive switching in metal oxide/organic semiconductor non-volatile memories as a critical phenomenon

    SciTech Connect (OSTI)

    Bory, Benjamin F.; Meskers, Stefan C. J.; Rocha, Paulo R. F.; Gomes, Henrique L.; Leeuw, Dago M. de

    2015-11-28

    Diodes incorporating a bilayer of an organic semiconductor and a wide bandgap metal oxide can show unipolar, non-volatile memory behavior after electroforming. The prolonged bias voltage stress induces defects in the metal oxide with an areal density exceeding 10{sup 17 }m{sup −2}. We explain the electrical bistability by the coexistence of two thermodynamically stable phases at the interface between an organic semiconductor and metal oxide. One phase contains mainly ionized defects and has a low work function, while the other phase has mainly neutral defects and a high work function. In the diodes, domains of the phase with a low work function constitute current filaments. The phase composition and critical temperature are derived from a 2D Ising model as a function of chemical potential. The model predicts filamentary conduction exhibiting a negative differential resistance and nonvolatile memory behavior. The model is expected to be generally applicable to any bilayer system that shows unipolar resistive switching.

  19. Determining the exchange parameters of spin-1 metal-organic molecular magnets in pulsed magnetic fields

    SciTech Connect (OSTI)

    Mcdonald, Ross D; Singleton, John; Lancaster, Tom; Goddard, Paul; Manson, Jamie

    2011-01-14

    We nave measured the high-field magnetization of a number of Ni-based metal-organic molecular magnets. These materials are self-assembly coordination polymers formed from transition metal ions and organic ligands. The chemistry of the compounds is versatile allowing many structures with different magnetic properties to be formed. These studies follow on from previous measurements of the Cu-based analogues in which we showed it was possible to extract the exchange parameters of low-dimensional magnets using pulsed magnetic fields. In our recent experiments we have investigated the compound (Ni(HF{sub 2})(pyz){sub 2})PF{sub 6}, where pyz = pyrazine, and the Ni-ions are linked in a quasi-two-dimensional (Q2D) square lattice via the pyrazine molecules, with the layers held together by HF{sub 2} ligands. We also investigated Ni(NCS){sub 2}(pyzdo){sub 2}, where pyzdo = pyrazine dioxide. The samples are grown at Eastern Washington University using techniques described elsewhere. Measurements are performed at the pulsed magnetic field laboratory in Los Alamos. The magnetization of powdered samples is determined using a compensated coil magnetometer in a 65 T short pulse magnet. Temperatures as low as 500 mK are achievable using a {sup 3}He cryostat. The main figure shows the magnetization of the spin-1 [Ni(HF{sub 2})(pyz){sub 2}]PF{sub 6} compound at 1.43 K. The magnetization rises slowly at first, achieving a rounded saturation whose midpoint is around 19 T. A small anomaly is also seen in the susceptibility at low fields ({approx}3 T), which might be attributed to a spin-flop transition. In contrast, the spin-1/2 [Cu(HF{sub 2})(pyz){sub 2}]PF{sub 6} measured previously has a saturation magnetization of 35.5 T and a strongly concave form of M(B) below this field. This latter compound was shown to be a good example of a Q2D Heisenberg antiferromagnet with the strong exchange coupling (J{sub 2D} = 12.4 K, J{sub {perpendicular}}/J{sub 2D} {approx} 10{sup -2}) directed along

  20. Synthesis, characterizations and catalytic studies of a new two-dimensional metal−organic framework based on Co–carboxylate secondary building units

    SciTech Connect (OSTI)

    Bagherzadeh, Mojtaba; Ashouri, Fatemeh; Đaković, Marijana

    2015-03-15

    A metal–organic framework [Co{sub 3}(BDC){sub 3}(DMF){sub 2}(H{sub 2}O){sub 2}] was synthesized and structurally characterized. X-ray single crystal analysis revealed that the framework contains a 2D polymeric chain through coordination of 1,4-benzenedicarboxylic acid linker ligand to cobalt centers. The polymer crystallize in monoclinic P2{sub 1}/n space group with a=13.989(3) Å, b=9.6728(17) Å, c=16.707(3) Å, and Z=2. The polymer features a framework based on the perfect octahedral Co–O6 secondary building units. The catalytic activities of [Co{sub 3}(BDC){sub 3}(DMF){sub 2}(H{sub 2}O){sub 2}]{sub n} for olefins oxidation was conducted. The heterogeneous catalyst could be facilely separated from the reaction mixture, and reused three times without significant degradation in catalytic activity. Furthermore, no contribution from homogeneous catalysis of active species leaching into reaction solution was detected. - Graphical abstract: A metal–organic framework of [Co{sub 3}(BDC){sub 3}(DMF){sub 2}(H{sub 2}O){sub 2}] was synthesized by hydrothermal method. This 2D-periodic framework is constructed from the infinite Co–O–C secondary building units and crystallizes in the monoclinic P2{sub 1}/n space group based on Co(II)–carboxylate units. The catalytic oxidation of various olefins was effectively carried out with [Co{sub 3}(BDC){sub 3}(DMF){sub 2}(H{sub 2}O){sub 2}]{sub n} catalyst by TBHP as oxidant. - Highlights: • A metal–organic framework of [Co{sub 3}(BDC){sub 3}(DMF){sub 2}(H{sub 2}O){sub 2}] is prepared by hydrothermal method. • The [Co{sub 3}(BDC){sub 3}(DMF){sub 2}(H{sub 2}O){sub 2}]{sub n} is constructed from Co–carboxylate secondary building units. • This coordination polymer displayed high catalytic activity for olefin oxidation reactions. • The catalytic reaction is heterogeneous and catalyst can be simply separated. • The heterogeneous catalyst can be reused several times without significant loss of catalytic activity.

  1. Geochemical Impacts of Carbon Dioxide, Brine, Trace Metal and Organic Leakage into an Unconfined, Oxidizing Limestone Aquifer

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Bacon, Diana H.; Dai, Zhenxue; Zheng, Liange

    2014-12-31

    An important risk at CO2 storage sites is the potential for groundwater quality impacts. As part of a system to assess the potential for these impacts a geochemical scaling function has been developed, based on a detailed reactive transport model of CO2 and brine leakage into an unconfined, oxidizing carbonate aquifer. Stochastic simulations varying a number of geochemical parameters were used to generate a response surface predicting the volume of aquifer that would be impacted with respect to regulated contaminants. The brine was assumed to contain several trace metals and organic contaminants. Aquifer pH and TDS were influenced by CO2more » leakage, while trace metal concentrations were most influenced by the brine concentrations rather than adsorption or desorption on calcite. Organic plume sizes were found to be strongly influenced by biodegradation.« less

  2. Theoretical Framework for Anomalous Heat Without High-Energy Particles from Deuteron Fusion in Deuterium-Transition Metal Systems

    SciTech Connect (OSTI)

    Scott R. Chubb; Talbot A. Chubb

    2000-11-12

    In cold fusion, two conflicting intuitive pictures have caused confusion. A local picture, involving particle-particle interaction, has been dominant for most physicists. However, we suggest that a second, nonlocal, 'counter-intuitive' picture is more appropriate because it places greater emphasis on the behavior of matter distributions and their interaction with the associated environment. This picture is relevant in solids because when charged particles possess large DeBroglie wavelengths, they frequently interact coherently, in a wavelike fashion, in which momentum is conserved globally but not locally. These wavelike effects can become important in periodically ordered solids since they may lead to large momentum transfer from an isolated location to many locations at once. The local picture fails to incorporate these kinds of effects. How hydrogen (H) nuclei can become delocalized is illustrated by anomalies in the diffusivity and vibrational behavior of H in transition metals. Also, it is well-known that in many-body systems, discontinuities in the local momentum (wave function cusps) can explain how near-perfect overlap between charged particles can occur at close separation (which may explain how the Coulomb barrier can be circumvented). We explore implications of these effects on cold fusion.

  3. One-pot synthesis of a metal–organic framework as an anode for Li-ion batteries with improved capacity and cycling stability

    SciTech Connect (OSTI)

    Gou, Lei Hao, Li-Min; Shi, Yong-Xin; Ma, Shou-Long; Fan, Xiao-Yong; Xu, Lei; Li, Dong-Lin Wang, Kang

    2014-02-15

    Metal–organic framework is a kind of novel electrode materials for lithium ion batteries. Here, a 3D metal–organic framework Co{sub 2}(OH){sub 2}BDC (BDC=1,4-benzenedicarboxylate) was synthesized for the first time by the reaction of Co{sup 2+} with a bio-inspired renewable organic ligand 1,4-benzenedicarboxylic acid through a solvothermal method. As an anode material for lithium ion batteries, this material exhibited an excellent cyclic stability as well as a large reversible capacity of ca. 650 mA h g{sup −1} at a current density of 50 mA g{sup −1} after 100 cycles within the voltage range of 0.02–3.0 V, higher than that of other BDC based anode. - Graphical abstract: The PXRD pattern and the cycleability curves (inset) of Co{sub 2}(OH){sub 2}BDC. Display Omitted - Highlights: • Co{sub 2}(OH){sub 2}BDC was synthesized through a one pot solvothermal process. • The solvent had a great effect on the purity of this material. • This material was used as anode material for lithium ion batteries for the first time. • Co{sub 2}(OH){sub 2}BDC showed improved capacity and cycling stability.

  4. Probing the Mechanism of CO2 Capture in Diamine-Appended Metal...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Probing the Mechanism of CO2 Capture in Diamine-Appended Metal-Organic Frameworks using Measured and Simulated X-ray Spectroscopy Previous Next List Drisdell, Walter S.; Poloni,...

  5. Sandia National Laboratories: ProjectOrganization

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Project Organization Task 1: Nanoscale framework for crack initiation and growth in body-centered cubic (bcc) transition metals The goal of this task is to develop an experimentally validated model for the earliest stages of ductile failure and initiation in bcc transition metals. The fundamentals of plasticity among bcc transition metals are studied through both simulation and experimental endeavors at the atomistic through nanometer length scales. Specific undertakings include: Atomistic

  6. Molecular Electronic Level Alignment at Weakly Coupled Organic Film/Metal Interfaces

    SciTech Connect (OSTI)

    Zhao, Jin; Feng, Min; Dougherty, Daniel B.; Sun, Hao; Petek, Hrvoje

    2014-10-28

    Electronic level alignment at interfaces of molecular materials with inorganic semiconductors and metals controls many interfacial phenomena. How the intrinsic properties of the interacting systems define the electronic structure of their interface remains one of the most important problems in molecular electronics and nanotechnology that can be solved through a combination of surface science experimental techniques and theoretical modeling. In this article, we address this fundamental problem through experimental and computational studies of molecular electronic level alignment of thin films of C6F6 on noble metal surfaces. The unoccupied electronic structure of C6F6 is characterized with single molecule resolution using low-temperature scanning tunneling microscopy-based constant-current distance-voltage spectroscopy. The experiments are performed on several noble metal surfaces with different work functions and distinct surface-normal projected band structures. In parallel, the electronic structures of the quantum wells (QWs) formed by the lowest unoccupied molecular orbital state of the C6F6 monolayer and multilayer films and their alignment with respect to the vacuum level of the metallic substrates are calculated by solving the Schrdinger equation for a semiempirical one-dimensional (1D) potential of the combined system using input from density functional theory. Our analysis shows that the level alignment for C6F6 molecules bound through weak van der Waals interactions to noble metal surfaces is primarily defined by the image potential of metal, the electron affinity of the molecule, and the molecule surface distance. We expect the same factors to determine the interfacial electronic structure for a broad range of molecule/metal interfaces.

  7. Selective adsorption in two porous triazolate–oxalate-bridged antiferromagnetic metal-azolate frameworks obtained via in situ decarboxylation of 3-amino-1,2,4-triazole-5-carboxylic acid

    SciTech Connect (OSTI)

    Hou, Juan-Juan; Xu, Xia; Jiang, Ning; Wu, Ya-Qin; Zhang, Xian-Ming

    2015-03-15

    Solvothermal reactions of metal salts, 3-amino-1,2,4-triazole-5-carboxylic acid (H{sub 2}atzc) and ammonium oxalate in different temperature produced two metal azolate frameworks, namely, [Cu{sub 3}(atzc){sub 2}(atz)(ox)]·1.5H{sub 2}O (1) and [Co{sub 5}(atz){sub 4}(ox){sub 3}(HCOO){sub 2}]·DMF (2) (H{sub 2}atzc=3-amino-1,2,4-triazole-5-carboxylic acid, Hatz=3-amino-1,2,4-triazole, and ox=oxalate), in which the atzc precusor was in situ decarboxylated. Structural determination reveals that 1 contains [Cu{sub 3}(atzc){sub 2}(atz)]{sup 2−} layers of mixed μ{sub 4}-atzc and μ{sub 3}-atz ligands, which are pillared by ox{sup 2−} groups to form a 3D porous framework. Compound 2 contains 2D layers with basic spindle-shaped decanuclear units, which extended by ox{sup 2−} and formates to form 3D porous framework. Gas adsorption investigation revealed that two kinds of frameworks exhibited selective CO{sub 2} over N{sub 2} sorption. Moreover, activated 2 shows H{sub 2} storage capacity. Additionally, magnetic properties of both the compounds have been investigated. - Graphical abstract: Solvothermal reactions of metal salts, 3-amino-1,2,4-triazole-5-carboxylate and oxalate produced two metal azolate frameworks, which could store gas molecules, especially H{sub 2} due to small pores. in situ decarboxylation of precursor was observed. - Highlights: • Two MAFs were synthesized via in situ decarboxylation of H{sub 2}atzc. • Both activated frameworks exhibited selective CO{sub 2} over N{sub 2} sorption. • Activated 2 could adsorb H{sub 2}, which makes it promising candidates for gas storage.

  8. Effect of landfill leachate organic acids on trace metal adsorption by kaolinite

    SciTech Connect (OSTI)

    Schroth, B.; Garrison, Sposito

    1997-02-01

    Hexanoic (hex) and fulvic acid (FA), representing early and later stages of landfill leachate evolution, were examined for influence on trace metal adsorption by a poorly crystallized kaolinite (KGa-2). Our experiments represented a model approach to examine possible reaction mechanisms in an environmentally important ternary metal-ligand-mineral surface system. Batch experiments were conducted in 0.01 mol kg(-1) NaClO4 at pH 3-8. Concentrations of metals (Cu, Cd, and Pb) and ligands were representative of those found typically in groundwater immediately downgradient of a landfill. The presence of FA resulted in enhancement of metal adsorption below pH 5, whereas the presence of hex produced no significant net change in metal uptake. Measured surface charge properties of KGa-2 were combined with binary and ternary system data in constructing a quantitative model of the system. The simple combination of binary system results was not effective in predicting the observed ternary system behavior. In both ternary systems, the addition of ternary surface complexes (TSCs) to the models resulted in a satisfactory fit to the data. Our work suggests the strong possibility that TSC involvement in surface reactions of natural adsorbents may be a useful concept.

  9. New electrolyte systems for capillary zone electrophoresis of metal cations and non-ionic organic compounds

    SciTech Connect (OSTI)

    Shi, Y.

    1995-06-19

    Excellent separations of metal ions can be obtained very quickly by capillary electrophoresis provided a weak complexing reagent is incorporated into the electrolyte to alter the effective mobilities of the sample ions. Indirect photometric detection is possible by also adding a UV-sensitive ion to the electrolyte. Separations are described using phthalate, tartrate, lactate or hydroxyisobutyrate as the complexing reagent. A separation of twenty-seven metal ions was achieved in only 6 min using a lactate system. A mechanism for the separation of lanthanides is proposed for the hydroxyisobutyrate system.

  10. The transformation of organic amines by transition metal cluster compounds: Progress report

    SciTech Connect (OSTI)

    Adams, R.D.

    1994-11-01

    Research during the current award period has covered several related topics which have emerged and grown as a consequence of the various discoveries that have been made during this award period. They have been divided into the following subsections for clarity and emphasis: The activation of tertiary amines by osmium cluster complexes; CH bond activation and ring opening of a nitrogen containing strained ring heterocycle by an osmium cluster complex; Ring opening of cyclic thioethers; cyclooligomerization of Thietanes; Studies of the cyclobutyne ligand; Insertion of an alkynes into metal-metal bonds; and Energy storage in metal clusters. A summary of the results of these studies is given in the following sections of this report. These studies have resulted in 50 scientific publications over the last three years and details of their studies beyond that given in the following sections can be found in those reports. All of these reports are listed in the final section of this report by the author`s names, title and journal citation.

  11. Metal inks

    DOE Patents [OSTI]

    Ginley, David S; Curtis, Calvin J; Miedaner, Alex; van Hest, Marinus Franciscus Antonius Maria; Kaydanova, Tatiana

    2014-02-04

    Self-reducing metal inks and systems and methods for producing and using the same are disclosed. In an exemplary embodiment, a method may comprise selecting metal-organic (MO) precursor, selecting a reducing agent, and dissolving the MO precursor and the reducing agent in an organic solvent to produce a metal ink that remains in a liquid phase at room temperature. Metal inks, including self-reducing and fire-through metal inks, are also disclosed, as are various applications of the metal inks.

  12. Fe-porphyrin-based metal–organic framework films as high-surface concentration, heterogeneous catalysts for electrochemical reduction of CO2

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Hod, Idan; Sampson, Matthew D.; Deria, Pravas; Kubiak, Clifford P.; Farha, Omar K.; Hupp, Joseph T.

    2015-09-18

    Realization of heterogeneous electrochemical CO2-to-fuel conversion via molecular catalysis under high-flux conditions requires the assembly of large quantities of reactant-accessible catalysts on conductive surfaces. As a proof of principle, we demonstrate that electrophoretic deposition of thin films of an appropriately chosen metal–organic framework (MOF) material is an effective method for immobilizing the needed quantity of catalyst. For electrocatalytic CO2 reduction, we used a material that contains functionalized Fe-porphyrins as catalytically competent, redox-conductive linkers. The approach yields a high effective surface coverage of electrochemically addressable catalytic sites (~1015 sites/cm2). The chemical products of the reduction, obtained with ~100% Faradaic efficiency, aremore » mixtures of CO and H2. The results validate the strategy of using MOF chemistry to obtain porous, electrode-immobilized, networks of molecular catalysts having competency for energy-relevant electrochemical reactions.« less

  13. Conductive open frameworks

    DOE Patents [OSTI]

    Yaghi, Omar M.; Wan, Shun; Doonan, Christian J.; Wang, Bo; Deng, Hexiang

    2016-02-23

    The disclosure relates generally to materials that comprise conductive covalent organic frameworks. The disclosure also relates to materials that are useful to store and separate gas molecules and sensors.

  14. Fabrication and characterization of organic solar cells using metal complex of phthalocyanines

    SciTech Connect (OSTI)

    Kida, Tomoyasu Suzuki, Atsushi Akiyama, Tsuyoshi Oku, Takeo

    2015-02-27

    Fabrication and characterization of organic solar cells using shuttle-cock-type phthalocyanines were carried out. Photovoltaic properties of the solar cells with inverted structures were investigated by current density-voltage characteristics. Effects of phase transition between H and J aggregates on the photovoltaic and optical properties were investigated. The photovoltaic mechanisms, energy levels and band gap of active layers were discussed.

  15. GTT Framework | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    DOE Grid Tech Team » GTT Framework GTT Framework GTT Framework Strategic Framework The GTT proposes a strategic framework that organizes these activities into three interrelated dimensions (informational, analytical, and physical), representative of the systems nature of the grid. Each of these dimensions have a corresponding strategic focus: The informational dimension aims to improve the visibility of grid conditions. The analytical dimension increases our understanding of the implications of

  16. Cognitive decision errors and organization vulnerabilities in nuclear power plant safety management: Modeling using the TOGA meta-theory framework

    SciTech Connect (OSTI)

    Cappelli, M.; Gadomski, A. M.; Sepiellis, M.; Wronikowska, M. W.

    2012-07-01

    In the field of nuclear power plant (NPP) safety modeling, the perception of the role of socio-cognitive engineering (SCE) is continuously increasing. Today, the focus is especially on the identification of human and organization decisional errors caused by operators and managers under high-risk conditions, as evident by analyzing reports on nuclear incidents occurred in the past. At present, the engineering and social safety requirements need to enlarge their domain of interest in such a way to include all possible losses generating events that could be the consequences of an abnormal state of a NPP. Socio-cognitive modeling of Integrated Nuclear Safety Management (INSM) using the TOGA meta-theory has been discussed during the ICCAP 2011 Conference. In this paper, more detailed aspects of the cognitive decision-making and its possible human errors and organizational vulnerability are presented. The formal TOGA-based network model for cognitive decision-making enables to indicate and analyze nodes and arcs in which plant operators and managers errors may appear. The TOGA's multi-level IPK (Information, Preferences, Knowledge) model of abstract intelligent agents (AIAs) is applied. In the NPP context, super-safety approach is also discussed, by taking under consideration unexpected events and managing them from a systemic perspective. As the nature of human errors depends on the specific properties of the decision-maker and the decisional context of operation, a classification of decision-making using IPK is suggested. Several types of initial situations of decision-making useful for the diagnosis of NPP operators and managers errors are considered. The developed models can be used as a basis for applications to NPP educational or engineering simulators to be used for training the NPP executive staff. (authors)

  17. SEME FRAMEWORK

    Energy Science and Technology Software Center (OSTI)

    003284MLTPL00 Sequentially Executed Model Evaluation Framework https://software.sandia.gov/svn/teva/canary

  18. Fe-porphyrin-based metal–organic framework films as high-surface concentration, heterogeneous catalysts for electrochemical reduction of CO2

    SciTech Connect (OSTI)

    Hod, Idan; Sampson, Matthew D.; Deria, Pravas; Kubiak, Clifford P.; Farha, Omar K.; Hupp, Joseph T.

    2015-09-18

    Realization of heterogeneous electrochemical CO2-to-fuel conversion via molecular catalysis under high-flux conditions requires the assembly of large quantities of reactant-accessible catalysts on conductive surfaces. As a proof of principle, we demonstrate that electrophoretic deposition of thin films of an appropriately chosen metal–organic framework (MOF) material is an effective method for immobilizing the needed quantity of catalyst. For electrocatalytic CO2 reduction, we used a material that contains functionalized Fe-porphyrins as catalytically competent, redox-conductive linkers. The approach yields a high effective surface coverage of electrochemically addressable catalytic sites (~1015 sites/cm2). The chemical products of the reduction, obtained with ~100% Faradaic efficiency, are mixtures of CO and H2. The results validate the strategy of using MOF chemistry to obtain porous, electrode-immobilized, networks of molecular catalysts having competency for energy-relevant electrochemical reactions.

  19. SU-E-I-02: A Framework to Perform Batch Simulations of Computational Voxel Phantoms to Study Organ Doses in Computed Tomography Using a Commercial Monte Carlo Software Package

    SciTech Connect (OSTI)

    Bujila, R; Nowik, P; Poludniowski, G

    2014-06-01

    Purpose: ImpactMC (CT Imaging, Erlangen, Germany) is a Monte Carlo (MC) software package that offers a GPU enabled, user definable and validated method for 3D dose distribution calculations for radiography and Computed Tomography (CT). ImpactMC, in and of itself, offers limited capabilities to perform batch simulations. The aim of this work was to develop a framework for the batch simulation of absorbed organ dose distributions from CT scans of computational voxel phantoms. Methods: The ICRP 110 adult Reference Male and Reference Female computational voxel phantoms were formatted into compatible input volumes for MC simulations. A Matlab (The MathWorks Inc., Natick, MA) script was written to loop through a user defined set of simulation parameters and 1) generate input files required for the simulation, 2) start the MC simulation, 3) segment the absorbed dose for organs in the simulated dose volume and 4) transfer the organ doses to a database. A demonstration of the framework is made where the glandular breast dose to the adult Reference Female phantom, for a typical Chest CT examination, is investigated. Results: A batch of 48 contiguous simulations was performed with variations in the total collimation and spiral pitch. The demonstration of the framework showed that the glandular dose to the right and left breast will vary depending on the start angle of rotation, total collimation and spiral pitch. Conclusion: The developed framework provides a robust and efficient approach to performing a large number of user defined MC simulations with computational voxel phantoms in CT (minimal user interaction). The resulting organ doses from each simulation can be accessed through a database which greatly increases the ease of analyzing the resulting organ doses. The framework developed in this work provides a valuable resource when investigating different dose optimization strategies in CT.

  20. Metal–organic frameworks assembled from lanthanide and 2,5-pyridinedicaboxylate with cubane-like [Ln{sub 4}(OH){sub 4}] building units

    SciTech Connect (OSTI)

    Abdelbaky, Mohammed S.M.; Amghouz, Zakariae; Fernández-Zapico, Eva; García-Granda, Santiago; García, José R.

    2015-09-15

    Lanthanide–organic frameworks based on 2,5-pyridinedicaboxylate (25p) ligand, formulated as [Yb{sub 4}(OH){sub 4}(25p){sub 4}(H{sub 2}O){sub 3}]·H{sub 2}O (25pYb), [Y{sub 4}(OH){sub 4}(25p){sub 4}(H{sub 2}O){sub 3}]·H{sub 2}O (25pY-1) and [Y{sub 6}(OH){sub 8}(25p){sub 5}(H{sub 2}O){sub 2}] (25pY-2), have been obtained as single phases under hydrothermal conditions. 25pYb and 25pY-1 are isostructural, and crystallize in the triclinic space group, P-1, with a=8.6075(5) Å, b=14.8478(7) Å, c=15.9164(9) Å, α=86.277(4)°, β=80.196(5)°, γ=81.785(4)°, and a=8.7166(6) Å, b=14.966(1) Å, c=15.966(1) Å, α=86.260(6)°, β=80.036(6)°, γ=81.599(6)°, respectively. 25pY-2 crystallizes in the monoclinic space group, P2{sub 1}/c, with a=24.9117(17) Å, b=13.7340(8) Å, c=14.3385(10) Å, β=100.551(7)°. 25pYb and 25pY-2 have been structurally characterized by single-crystal X-ray diffraction. The 25pYb structure is based on tetranuclear cubane-like [Yb{sub 4}(OH){sub 4}]{sup 8+} clusters, which are interconnected to eight neighbouring clusters through teen surrounding 25p ligands leading to neutral 3D framework, while the structure of 25pY-2 is based on two independent cuban-like [Y{sub 4}(OH){sub 4}]{sup 8+} clusters, which are joined together through Y1 cation leading to the formation of hexanuclear [Y{sub 6}(OH){sub 8}]{sup 10+} clusters, which in turn are joined via Y2 cation resulting in infinite inorganic chain extending along c-axis, and each chain is interconnected to six adjacent chains through 25p ligands leading finally to 3D framework. The luminescence properties of Eu{sup 3+} and Tb{sup 3+} doped 25pY-1 and 25pY-2 compounds have also been investigated. All materials has been characterized by powder X-ray diffraction, thermal analyses (TG–SDTA–MS), FTIR spectroscopy, C–H–N elemental analysis, scanning electron microscopy (SEM-EDX), and powder X-ray thermodiffraction. - Graphical abstract: Nowadays, lanthanide–organic frameworks (LOFs) attract

  1. Organic metal neutron detector

    DOE Patents [OSTI]

    Butler, Michael A.; Ginley, David S.

    1987-01-01

    A device for detecting neutrons comprises a layer of conductive polymer sandwiched between electrodes, which may be covered on each face with a neutron transmissive insulating material layer. Conventional electrodes are used for a non-imaging integrating total neutron fluence-measuring embodiment, while wire grids are used in an imaging version of the device. The change in conductivity of the polymer after exposure to a neutron flux is determined in either case to provide the desired data. Alternatively, the exposed conductive polymer layer may be treated with a chemical reagent which selectively binds to the sites altered by neutrons to produce an image of the flux detected.

  2. Spectral, mechanical, thermal, optical and solid state parameters, of metal-organic bis(hydrogenmaleate)-CO(II) tetrahydrate crystal

    SciTech Connect (OSTI)

    Chandran, Senthilkumar; Jagan, R.; Paulraj, Rajesh; Ramasamy, P.

    2015-10-15

    Metal-organic bis(hydrogenmaleate)-Co(II) tetrahydrate single crystals have been grown by slow evaporation solution growth technique at room temperature. The crystal structure and the unit cell parameters were analyzed from the X-ray diffraction studies. Single-crystal X-ray diffraction analyses reveal that the grown crystal belongs to triclinic system with the space group P-1. Functional groups in bis(hydrogenmaleate)-Co(II) tetrahydrate were identified by Fourier transform infrared spectral analysis. The peak observed at 663 cm{sup −1} is assigned to the (Co–O) stretching vibrations. The optical transmission of the crystal was studied by UV–vis–NIR spectral analysis. The photoluminescence emission studies were carried out for the title compound in a wide wavelength range between 350 nm and 550 nm at 303 K. Mechanical strength was tested by Vickers microhardness test. The laser damage threshold value has been determined using Nd:YAG laser operating at 1064 nm. At various frequencies and temperatures the dielectric behavior of the material was investigated. Solid state parameters such as plasma energy, Penn gap, Fermi energy and electronic polarizability were evaluated. Photoconductivity measurements were carried out for the grown crystal in the presence of DC electric field at room temperature. Thermal stability and decomposition of the crystal were studied by TG–DTA. The weight loss of the title compound occurs in different steps. - Graphical abstract: Molecular structure of the bis(hydrogenmaleate)-Co(II) tetrahydrate drawn at 40% ellipsoid probability level. - Highlights: • Bis(hydrogenmaleate)-Co(II) tetrahydrate single crystal is grown by slow evaporation method. • Structural and optical properties were discussed. • The title complex crystal is thermally stable up to 91 °C. • Plasma energy, Fermi energy and electronic polarizability are evaluated. • It exhibits positive photoconductivity.

  3. Inorganic–organic hybrids presenting high basic center content: SBA-15 incorporation, toxic metals sorption and energetic behavior

    SciTech Connect (OSTI)

    Oliveira, Fernando J.V.E.; Melo, Maurício A.; Airoldi, Claudio

    2013-03-15

    Highlights: ► Mesoporous SBA-15 silicas were organofunctionalized with new silylant agents. ► Thiocarbamate was used to enhance the silylating agent chains and basic centers. ► The synthesized pendant chains contain nitrogen and sulfur basic centers. ► The new hybrids sorb toxic cations from aqueous solutions with high efficiency. ► The thermodynamic data demonstrated favorable cation/basic center interactions. - Abstract: Mesoporous SBA-15 samples were organofunctionalized with mono, di- and tri-aminosilanes that previously reacted with thiocarbamide to enhance the organic chains and attach nitrogen and sulfur basic centers to the surface of the solids. These new organosilanes were synthesized through a non-solvent approach to reduce both cost and hazardous wastes. The high affinities for both hard and soft Lewis acids due to the combination of nitrogen and sulfur atoms attached to the same pendant chain enabled favorable sorption capacities for Cu{sup 2+}, Cd{sup 2+} and Pb{sup 2+} cations, with maximum capacities of 1.90, 3.48 and 5.30 mmol g{sup −1}, respectively, for the most efficient mesoporous silica. Microcalorimetric investigations allowed the calculation of the thermodynamic data at the solid/liquid interface. All Gibbs energy are negative as expected for spontaneous cation/basic center interactions and the positive entropic values from 49 ± 3 to 108 ± 5 J K{sup −1} mol{sup −1}, also reinforced this favorable interactive process in heterogeneous system. The designed organosilanes covalently bonded to the inorganic siliceous skeleton can be suggested as new materials for toxic metal removal from a wastewater with high efficiency.

  4. MVC Framework

    Energy Science and Technology Software Center (OSTI)

    2008-06-03

    Provides a reusable model-view-controller application programming interface (API) for use in the rapid development of graphical user interface applications in the .NET 2.0 framework. This includes a mechanism for adding new data stores, data sources, data analyses, and visualizations in the form of plugins.] The MVC Framework is implemented in C# as a .NET 2.0 framework that can then be built against when developing applications. The infrasturcture allows for presenting application specific views (visualizations) tomore » the user to interact with. Based on the interactions the suer makes with a view, requests are generated which in turn are handled by the central controller facility. The controller handles the request in an application specific manner by routing the request to appropriate data stores, data accessors or data analyzers. Retrieved or processed data is published to subscribed components for further processing or for presentation to the user.« less

  5. High-Throughput Methodology for Discovery of Metal-Organic Frameworks with a High Binding Energy (New Joint UC-Berkeley/Symyx DoD/DLA Project) (presentation)

    Broader source: Energy.gov [DOE]

    Presented at the U.S. Department of Energy's Hydrogen Storage Meeting held June 26, 2007 in Bethesda, Maryland.

  6. Fluorocarbon Adsorption in Hierarchical Porous Frameworks

    SciTech Connect (OSTI)

    Motkuri, Radha K.; Annapureddy, Harsha V.; Vijayakumar, M.; Schaef, Herbert T.; Martin, P F.; McGrail, B. Peter; Dang, Liem X.; Krishna, Rajamani; Thallapally, Praveen K.

    2014-07-09

    The adsorption behavior of a series of fluorocarbon derivatives was examined on a set of microporous metal organic framework (MOF) sorbents and another set of hierarchical mesoporous MOFs. The microporous M-DOBDC (M = Ni, Co) showed a saturation uptake capacity for R12 of over 4 mmol/g at a very low relative saturation pressure (P/Po) of 0.02. In contrast, the mesoporous MOF MIL-101 showed an exceptionally high uptake capacity reaching over 14 mmol/g at P/Po of 0.4. Adsorption affinity in terms of mass loading and isosteric heats of adsorption were found to generally correlate with the polarizability of the refrigerant with R12 > R22 > R13 > R14 > methane. These results suggest the possibility of exploiting MOFs for separation of azeotropic mixtures of fluorocarbons and use in eco-friendly fluorocarbon-based adsorption cooling and refrigeration applications.

  7. A new zinc-1,3,5-benzenetricarboxylate framework integrated three distinct subunits (SBUs)

    SciTech Connect (OSTI)

    Xie, Yi-Ming

    2013-06-01

    A new metal-organic framework (MOF) [Zn₅(btc)₃(H₂O)₀.₅(O)₀.₅(DMA)₃]·1.75(DMA) (1; btc=1,3,5-benzenetricarboxylate; DMA=N,N´-dimethyl acetamide) has been solvothermally synthesized. Unusually, three distinct subunits (SBUs), [Zn₂(CO₂)₄(DMA)₂], [(μ₃-H₂O)Zn₃(CO₂)₆(DMA)] and [(µ₄-O)Zn₄(CO₂)₆(DMA)₂] are observed in 1 simultaneously. The integration of three distinct SBUs leads to an interesting Zn-btc framework materials with unusual structural topology. - Graphical abstract: Presented here is a new zinc-1,3,5-benzenetricarboxylate framework integrated three distinct subunits (SBUs). - Highlights: • A new zinc-1,3,5-benzenetricarboxylate framework has been synthesized. • Three distinct subunits (SBUs) are observed in 1 simultaneously. • The integration of three distinct SBUs leads to an unusual structural topology.

  8. High Electrical Conductivity in Ni3(2,3,6,7,10,11-hexaiminotriphenylene)2, a Semiconducting Metal-Organic Graphene Analogue

    SciTech Connect (OSTI)

    Sheberla, Dennis; Sun, Lei; Blood-Forsythe, Martin A.; Er, Süleyman; Wade, Casey R.; Brozek, Carl K.; Aspuru-Guzik, Alán; Dinc,; #259; Mircea,

    2014-09-22

    Reaction of 2,3,6,7,10,11-hexaaminotriphenylene with Ni2+ in aqueous NH3 solution under aerobic conditions produces Ni3(HITP)2 (HITP = 2,3,6,7,10,11-hexaiminotriphenylene), a new two-dimensional metal–organic framework (MOF). The new material can be isolated as a highly conductive black powder or dark blue-violet films. Two-probe and van der Pauw electrical measurements reveal bulk (pellet) and surface (film) conductivity values of 2 and 40 S·cm–1, respectively, both records for MOFs and among the best for any coordination polymer.

  9. V&V framework

    SciTech Connect (OSTI)

    Hills, Richard G.; Maniaci, David Charles; Naughton, Jonathan W.

    2015-09-01

    A Verification and Validation (V&V) framework is presented for the development and execution of coordinated modeling and experimental program s to assess the predictive capability of computational models of complex systems through focused, well structured, and formal processes.The elements of the framework are based on established V&V methodology developed by various organizations including the Department of Energy, National Aeronautics and Space Administration, the American Institute of Aeronautics and Astronautics, and the American Society of Mechanical Engineers. Four main topics are addressed: 1) Program planning based on expert elicitation of the modeling physics requirements, 2) experimental design for model assessment, 3) uncertainty quantification for experimental observations and computational model simulations, and 4) assessment of the model predictive capability. The audience for this document includes program planners, modelers, experimentalist, V &V specialist, and customers of the modeling results.

  10. Metals 2000

    SciTech Connect (OSTI)

    Allison, S.W.; Rogers, L.C.; Slaughter, G.; Boensch, F.D.; Claus, R.O.; de Vries, M.

    1993-05-01

    This strategic planning exercise identified and characterized new and emerging advanced metallic technologies in the context of the drastic changes in global politics and decreasing fiscal resources. In consideration of a hierarchy of technology thrusts stated by various Department of Defense (DOD) spokesmen, and the need to find new and creative ways to acquire and organize programs within an evolving Wright Laboratory, five major candidate programs identified are: C-17 Flap, Transport Fuselage, Mach 5 Aircraft, 4.Fighter Structures, and 5. Missile Structures. These results were formed by extensive discussion with selected major contractors and other experts, and a survey of advanced metallic structure materials. Candidate structural applications with detailed metal structure descriptions bracket a wide variety of uses which warrant consideration for the suggested programs. An analysis on implementing smart skins and structures concepts is given from a metal structures perspective.

  11. Temperature dependent structural variation from 2D supramolecular network to 3D interpenetrated metal–organic framework: In situ cleavage of S–S and C–S bonds

    SciTech Connect (OSTI)

    Ugale, Bharat; Singh, Divyendu; Nagaraja, C.M.

    2015-03-15

    Two new Zn(II)–organic compounds, [Zn(muco)(dbds){sub 2}(H{sub 2}O){sub 2}] (1) and [Zn(muco)(dbs)] (2) (where, muco=trans, trans-muconate dianion, dbds=4,4′-dipyridyldisulfide and dbs=4,4′-dipyridylsulfide) have been synthesized from same precursors but at two different temperatures. Both the compounds have been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, IR spectroscopy, thermal analysis and photoluminescence studies. Compound 1 prepared at room temperature possesses a molecular structure extended to 2D supramolecular network through (H–O…H) hydrogen-bonding interactions. Compound 2, obtained at high temperature (100 °C) shows a 3-fold interpenetrating 3D framework constituted by an in situ generated dbs linker by the cleavage of S–S and C–S bonds of dbds linker. Thus, the influence of reaction temperature on the formation of two structural phases has been demonstrated. Both 1 and 2 exhibit ligand based luminescence emission owing to n→π⁎ and π→π⁎ transitions and also high thermal stabilities. - Graphical abstract: The influence of temperature on the formation of two structural phases, a 2D supramolecular network and a 3D 3-fold interpenetrating framework has been demonstrated and their luminescence emission is measured. - Highlights: • Two new Zn(II)–organic compounds were synthesized by tuning reaction temperatures. • Temperature induced in situ generation of dbs linker has been observed. • The compounds exhibit high thermal stability and luminescence emission properties. • The effect of temperature on structure, dimension and topology has been presented.

  12. Effect of metal in M3(btc)2 and M2(dobdc) MOFs for O2/N2 separations: A combined density functional theory and experimental study

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Parkes, Marie V.; Sava Gallis, Dorina F.; Greathouse, Jeffery A.; Nenoff, Tina M.

    2015-03-02

    Computational screening of metal-organic framework (MOF) materials for selective oxygen adsorption from air could lead to new sorbents for the oxyfuel combustion process feedstock streams. A comprehensive study on the effect of MOF metal chemistry on gas binding energies in two common but structurally disparate metal-organic frameworks has been undertaken. Dispersion-corrected density functional theory methods were used to calculate the oxygen and nitrogen binding energies with each of fourteen metals, respectively, substituted into two MOF series, M2(dobdc) and M3(btc)2. The accuracy of DFT methods was validated by comparing trends in binding energy with experimental gas sorption measurements. A periodic trendmore » in oxygen binding energies was found, with greater oxygen binding energies for early transition-metal-substituted MOFs compared to late transition metal MOFs; this was independent of MOF structural type. The larger binding energies were associated with oxygen binding in a side-on configuration to the metal, with concomitant lengthening of the O-O bond. In contrast, nitrogen binding energies were similar across the transition metal series, regardless of both MOF structural type and metal identity. Altogether, these findings suggest that early transition metal MOFs are best suited to separating oxygen from nitrogen, and that the MOF structural type is less important than the metal identity.« less

  13. Effects of growth temperature on the properties of InGaN channel heterostructures grown by pulsed metal organic chemical vapor deposition

    SciTech Connect (OSTI)

    Zhang, Yachao; Zhou, Xiaowei; Xu, Shengrui; Wang, Zhizhe; Chen, Zhibin; Zhang, Jinfeng; Zhang, Jincheng E-mail: xd-zhangyachao@163.com; Hao, Yue E-mail: xd-zhangyachao@163.com

    2015-12-15

    Pulsed metal organic chemical vapor deposition (P-MOCVD) is introduced into the growth of high quality InGaN channel heterostructures. The effects of InGaN channel growth temperature on the structural and transport properties of the heterostructures are investigated in detail. High resolution x-ray diffraction (HRXRD) and Photoluminescence (PL) spectra indicate that the quality of InGaN channel strongly depends on the growth temperature. Meanwhile, the atomic force microscopy (AFM) results show that the interface morphology between the InGaN channel and the barrier layer also relies on the growth temperature. Since the variation of material properties of InGaN channel has a significant influence on the electrical properties of InAlN/InGaN heterostructures, the optimal transport properties can be achieved by adjusting the growth temperature. A very high two dimension electron gas (2DEG) density of 1.92 × 10{sup 13} cm{sup −2} and Hall electron mobility of 1025 cm{sup 2}/(V⋅s) at room temperature are obtained at the optimal growth temperature around 740 °C. The excellent transport properties in our work indicate that the heterostructure with InGaN channel is a promising candidate for the microwave power devices, and the results in this paper will be instructive for further study of the InGaN channel heterostructures.

  14. Low-temperature growth and orientational control in RuO{sub 2} thin films by metal-organic chemical vapor deposition

    SciTech Connect (OSTI)

    Bai, G.R.; Wang, A.; Foster, C.M.; Vetrone, J.; Patel, J.; Wu, X.

    1996-08-01

    For growth temperatures in the range of 275 C to 425 C, highly conductive RuO{sub 2} thin films with either (110)- or (101)-textured orientations have been grown by metal-organic chemical vapor deposition (MOCVD) on both SiO{sub 2}/Si(001) and Pt/Ti/SiO{sub 2}/Si(001) substrates. Both the growth temperature and growth rate were used to control the type and degree of orientational texture of the RuO{sub 2} films. In the upper part of this growth temperature range ({approximately} 350 C) and at a low growth rate (< 30 {angstrom}/min.), the RuO{sub 2} films favored a (110)-textured. In contrast, at the lower part of this growth temperature range ({approximately} 300 C) and at a high growth rate (> 30 {angstrom}/min.), the RuO{sub 2} films favored a (101)-textured. In contrast, a higher growth temperatures (> 425 C) always produced randomly-oriented polycrystalline films. For either of these low-temperature growth processes, the films produced were crack-free, well-adhered to the substrates, and had smooth, specular surfaces. Atomic force microscopy showed that the films had a dense microstructure with an average grain size of 50--80 nm and a rms. surface roughness of {approximately} 3--10 nm. Four-probe electrical transport measurements showed that the films were highly conductive with resistivities of 34--40 {micro}{Omega}-cm ({at} 25 C).

  15. Relaxation and critical strain for maximum In incorporation in AlInGaN on GaN grown by metal organic vapour phase epitaxy

    SciTech Connect (OSTI)

    Reuters, Benjamin; Finken, M.; Wille, A.; Kalisch, H.; Vescan, A.; Hollaender, B.; Heuken, M.

    2012-11-01

    Quaternary AlInGaN layers were grown on conventional GaN buffer layers on sapphire by metal organic vapour phase epitaxy at different surface temperatures and different reactor pressures with constant precursor flow conditions. A wide range in compositions within 30-62% Al, 5-29% In, and 23-53% Ga was covered, which leads to different strain states from high tensile to high compressive. From high-resolution x-ray diffraction and Rutherford backscattering spectrometry, we determined the compositions, strain states, and crystal quality of the AlInGaN layers. Atomic force microscopy measurements were performed to characterize the surface morphology. A critical strain value for maximum In incorporation near the AlInGaN/GaN interface is presented. For compressively strained layers, In incorporation is limited at the interface as residual strain cannot exceed an empirical critical value of about 1.1%. Relaxation occurs at about 15 nm thickness accompanied by strong In pulling. Tensile strained layers can be grown pseudomorphically up to 70 nm at a strain state of 0.96%. A model for relaxation in compressively strained AlInGaN with virtual discrete sub-layers, which illustrates the gradually changing lattice constant during stress reduction is presented.

  16. Enterprise Risk Management Framework

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Framework The Enterprise Risk Management (ERM) framework includes four steps: identify the risks, determine the probability and impact of each one, identify controls that are...

  17. The influence of pressure on the photoluminescence properties of a terbium-adipate framework

    SciTech Connect (OSTI)

    Spencer, Elinor C.; Zhao, Jing; Ross, Nancy L.; Andrews, Michael B.; Surbella, Robert G.; Cahill, Christopher L.

    2013-06-15

    The influence of pressure (over the 0–4.7 GPa range) on the photoluminescence emissions and crystal structure of the known 3D terbium-adipate metal-organic framework material Tb-GWMOF6 has been evaluated by high-pressure single-crystal X-ray diffraction and spectroscopic techniques. The results from this study show that this complex lanthanide framework structure undergoes three phase transitions within the 0–4 GPa pressure range that involve alterations in the number of symmetry independent Tb{sup 3+} ion sites within the crystal lattice. These pressure induced modifications to the structure of Tb-GWMOF6 lead to pronounced changes in the profiles of the {sup 5}D{sub 4}→{sup 7}F{sub 5} emission spectra of this complex. - Graphical abstract: The influence of pressure on the structure and photoluminescence emissions of a 3D terbium-adipate framework. - Highlights: • High-pressure luminescence spectra for a Tb framework were collected. • High-pressure single-crystal XRD experiments were conducted with the Tb Framework. • The framework undergoes two pressure-induced phase transitions. • The three phases of the material show different photoluminescence behaviour.

  18. Tuning Reactivity and Electronic Properties through Ligand Reorganization within a Cerium Heterobimetallic Framework

    SciTech Connect (OSTI)

    Robinson, Jerome R.; Gordon, Zachary; Booth, Corwin H.; Carroll, Patrick J.; Walsh, Patrick J.; Schelter, Eric J.

    2014-06-24

    Cerium compounds have played vital roles in organic, inorganic, and materials chemistry due to their reversible redox chemistry between trivalent and tetravalent oxidation states. However, attempts to rationally access molecular cerium complexes in both oxidation states have been frustrated by unpredictable reactivity in cerium(III) oxidation chemistry. Such oxidation reactions are limited by steric saturation at the metal ion, which can result in high energy activation barriers for electron transfer. An alternative approach has been realized using a rare earth/alkali metal/1,1'-BINOLate (REMB) heterobimetallic framework, which uses redox-inactive metals within the secondary coordination sphere to control ligand reorganization. The rational syntheses of functionalized cerium(IV) products and a mechanistic examination of the role of ligand reorganization in cerium(III) oxidation are presented.

  19. Reversible photodeposition and dissolution of metal ions

    DOE Patents [OSTI]

    Foster, Nancy S.; Koval, Carl A.; Noble, Richard D.

    1994-01-01

    A cyclic photocatalytic process for treating waste water containing metal and organic contaminants. In one embodiment of the method, metal ions are photoreduced onto the photocatalyst and the metal concentrated by resolubilization in a smaller volume. In another embodiment of the method, contaminant organics are first oxidized, then metal ions removed by photoreductive deposition. The present invention allows the photocatalyst to be recycled until nearly complete removal of metal ions and organic contaminants is achieved.

  20. Integrated Global System Modeling Framework | Open Energy Information

    Open Energy Info (EERE)

    System Modeling Framework AgencyCompany Organization: MIT Joint Program on the Science and Policy of Global Change Sector: Climate, Energy Focus Area: Renewable Energy...

  1. Ghana-Support for Future National Climate Change Policy Framework...

    Open Energy Info (EERE)

    Jump to: navigation, search Name CDKN-Ghana-Support for Future National Climate Change Policy Framework AgencyCompany Organization Climate and Development Knowledge Network...

  2. Organization | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Organization Organization Organization

  3. Computational Design of Metal Ion Sequestering Agents

    SciTech Connect (OSTI)

    Hay, Benjamin P.; Rapko, Brian M.

    2005-06-15

    Organic ligands that exhibit a high degree of metal ion recognition are essential precursors for developing separation processes and sensors for metal ions. Since the beginning of the nuclear era, much research has focused on discovering ligands that target specific radionuclides. Members of the Group 1A and 2A cations (e.g., Cs, Sr, Ra) and the f-block metals (actinides and lanthanides) are of primary concern to DOE. Although there has been some success in identifying ligand architectures that exhibit a degree of metal ion recognition, the ability to control binding affinity and selectivity remains a significant challenge. The traditional approach for discovering such ligands has involved lengthy programs of organic synthesis and testing that, in the absence of reliable methods for screening compounds before synthesis, have resulted in much wasted research effort. This project seeks to enhance and strengthen the traditional approach through computer-aided design of new and improved host molecules. Accurate electronic structure calculations are coupled with experimental data to provide fundamental information about ligand structure and the nature of metal-donor group interactions (design criteria). This fundamental information then is used in a molecular mechanics model (MM) that helps us rapidly screen proposed ligand architectures and select the best members from a set of potential candidates. By using combinatorial methods, molecule building software has been developed that generates large numbers of candidate architectures for a given set of donor groups. The specific goals of this project are: further understand the structural and energetic aspects of individual donor group- metal ion interactions and incorporate this information within the MM framework further develop and evaluate approaches for correlating ligand structure with reactivity toward metal ions, in other words, screening capability use molecule structure building software to generate large

  4. Multi-scale framework for the accelerated design of high-efficiency...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Multi-scale framework for the accelerated design of high-efficiency organic photovoltaic cells Organic and hybrid organicinorganic solar cells (OSC) offer a promising low-cost...

  5. Effect of metal in M3(btc)2 and M2(dobdc) MOFs for O2/N2 separations: A combined density functional theory and experimental study

    SciTech Connect (OSTI)

    Parkes, Marie V.; Sava Gallis, Dorina F.; Greathouse, Jeffery A.; Nenoff, Tina M.

    2015-03-02

    Computational screening of metal-organic framework (MOF) materials for selective oxygen adsorption from air could lead to new sorbents for the oxyfuel combustion process feedstock streams. A comprehensive study on the effect of MOF metal chemistry on gas binding energies in two common but structurally disparate metal-organic frameworks has been undertaken. Dispersion-corrected density functional theory methods were used to calculate the oxygen and nitrogen binding energies with each of fourteen metals, respectively, substituted into two MOF series, M2(dobdc) and M3(btc)2. The accuracy of DFT methods was validated by comparing trends in binding energy with experimental gas sorption measurements. A periodic trend in oxygen binding energies was found, with greater oxygen binding energies for early transition-metal-substituted MOFs compared to late transition metal MOFs; this was independent of MOF structural type. The larger binding energies were associated with oxygen binding in a side-on configuration to the metal, with concomitant lengthening of the O-O bond. In contrast, nitrogen binding energies were similar across the transition metal series, regardless of both MOF structural type and metal identity. Altogether, these findings suggest that early transition metal MOFs are best suited to separating oxygen from nitrogen, and that the MOF structural type is less important than the metal identity.

  6. Molecular dynamics simulation of framework flexibility effects on noble gas diffusion in HKUST-1 and ZIF-8

    SciTech Connect (OSTI)

    Parkes, Marie V.; Demir, Hakan; Teich-McGoldrick, Stephanie L.; Sholl, David S.; Greathouse, Jeffery A.; Allendorf, Mark D.

    2014-03-28

    Molecular dynamics simulations were used to investigate trends in noble gas (Ar, Kr, Xe) diffusion in the metal-organic frameworks HKUST-1 and ZIF-8. Diffusion occurs primarily through inter-cage jump events, with much greater diffusion of guest atoms in HKUST-1 compared to ZIF-8 due to the larger cage and window sizes in the former. We compare diffusion coefficients calculated for both rigid and flexible frameworks. For rigid framework simulations, in which the framework atoms were held at their crystallographic or geometry optimized coordinates, sometimes dramatic differences in guest diffusion were seen depending on the initial framework structure or the choice of framework force field parameters. When framework flexibility effects were included, argon and krypton diffusion increased significantly compared to rigid-framework simulations using general force field parameters. Additionally, for argon and krypton in ZIF-8, guest diffusion increased with loading, demonstrating that guest-guest interactions between cages enhance inter-cage diffusion. No inter-cage jump events were seen for xenon atoms in ZIF-8 regardless of force field or initial structure, and the loading dependence of xenon diffusion in HKUST-1 is different for rigid and flexible frameworks. Diffusion of krypton and xenon in HKUST-1 depends on two competing effects: the steric effect that decreases diffusion as loading increases, and the “small cage effect” that increases diffusion as loading increases. Finally, a detailed analysis of the window size in ZIF-8 reveals that the window increases beyond its normal size to permit passage of a (nominally) larger krypton atom.

  7. Enterprise Risk Management Framework

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Framework The Enterprise Risk Management (ERM) framework includes four steps: identify the risks, determine the probability and impact of each one, identify controls that are already in place that mitigate that risk, and propose additional controls if needed. Step 1: Identify Risks - What can go wrong? This step should identify the negative outcomes that could result from an action or decision . It is important to consider a wide range of risks, and so the Department's ERM framework includes

  8. CBI Technology Impact Framework

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    CBI Technology Impact Framework 2014 Building Technologies Office Peer Review Images courtesy CREE, True Manufacturing, A.O. Smith, Bernstein Associates, Cambridge Engineering, ...

  9. Metal aminoboranes

    DOE Patents [OSTI]

    Burrell, Anthony K.; Davis, Benjamin J.; Thorn, David L.; Gordon, John C.; Baker, R. Thomas; Semelsberger, Troy Allen; Tumas, William; Diyabalanage, Himashinie Vichalya Kaviraj; Shrestha, Roshan P.

    2010-05-11

    Metal aminoboranes of the formula M(NH.sub.2BH.sub.3).sub.n have been synthesized. Metal aminoboranes are hydrogen storage materials. Metal aminoboranes are also precursors for synthesizing other metal aminoboranes. Metal aminoboranes can be dehydrogenated to form hydrogen and a reaction product. The reaction product can react with hydrogen to form a hydrogen storage material. Metal aminoboranes can be included in a kit.

  10. Metal dusting

    SciTech Connect (OSTI)

    Edited by K. Natesan

    2004-01-01

    This workshop was held soon after the September 11th incident under a climate of sorrow and uncertainty among the people of the world, in particular the Workshop participants and their host organizations. With considerable help from the partiicpants, the Workshop was conducted as planed and we had excellent participation in spite of the circumstances. A good fraction of the attendees in the Workshop were from abroad and from several industries, indicating the importance and relevance of the subject for the chemical process industry. Degradation of structural metallic alloys by metal dusting has been an issue for over 40 years in the chemical, petrochemical, syngas, and iron ore reduction plants. However, the fundamental scientific reasons for the degradation of complex alloys in high carbon activity environments are not clear. one of the major parameters of importance is the variation in gas chemistry in both the laboratory experiments and in the plant-service environments. the industry has questioned the applicability of the laboratory test data, obtained in low steam environments, in assessment and life prediction for the materials in plant service where the environments contain 25-35% steam. Several other variables such as system pressure, gas flow velocity, incubation time, alloy chemistry, surface finish, and weldments, were also identified in the literature as to having an effect on the initiatino and propagation of metal dusting attack. It is the purpose of this Workshop to establish a forum in which the researchers from scientific and industrial laboratories, alloy manufacturers, end users, and research and development sponsors can exchange information, discuss different points of view, prioritize the issues, and to elaborate on the trends in industry for the future. We believe that we accomplished these goals successfully and sincerely thank the participants for their contributions.

  11. Standard Agent Framework 1

    Energy Science and Technology Software Center (OSTI)

    1999-04-06

    The Standard Agent framework provides an extensible object-oriented development environment suitable for use in both research and applications projects. The SAF provides a means for constructing and customizing multi-agent systems through specialization of standard base classes (architecture-driven framework) and by composition of component classes (data driven framework). The standard agent system is implemented as an extensible object-centerd framework. Four concrete base classes are developed: (1) Standard Agency; (2) Standard Agent; (3) Human Factor, and (4)more » Resources. The object-centered framework developed and utilized provides the best comprimise between generality and flexibility available in agent development systems today.« less

  12. Inverted organic photosensitive device

    SciTech Connect (OSTI)

    Forrest, Stephen R.; Tong, Xiaoran; Lee, Jun Yeob; Cho, Yong Joo

    2015-09-08

    There is disclosed a method for preparing the surface of a metal substrate. The present disclosure also relates to an organic photovoltaic device including a metal substrate made by such method. Also disclosed herein is an inverted photosensitive device including a stainless steel foil reflective electrode, an organic donor-acceptor heterojunction over the reflective electrode, and a transparent electrode over the donor-acceptor heterojunction.

  13. Oxygen reduction reaction: A framework for success

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Allendorf, Mark D.

    2016-05-06

    Oxygen reduction at the cathode of fuel cells typically requires a platinum-based material to catalyse the reaction, but lower-cost, more stable catalysts are sought. Here, an intrinsically conductive metal–organic framework based on cheaper elements is shown to be a durable, structurally well-defined catalyst for this reaction.

  14. Molecular dynamics simulation of framework flexibility effects on noble gas diffusion in HKUST-1 and ZIF-8

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Parkes, Marie V.; Demir, Hakan; Teich-McGoldrick, Stephanie L.; Sholl, David S.; Greathouse, Jeffery A.; Allendorf, Mark D.

    2014-03-28

    Molecular dynamics simulations were used to investigate trends in noble gas (Ar, Kr, Xe) diffusion in the metal-organic frameworks HKUST-1 and ZIF-8. Diffusion occurs primarily through inter-cage jump events, with much greater diffusion of guest atoms in HKUST-1 compared to ZIF-8 due to the larger cage and window sizes in the former. We compare diffusion coefficients calculated for both rigid and flexible frameworks. For rigid framework simulations, in which the framework atoms were held at their crystallographic or geometry optimized coordinates, sometimes dramatic differences in guest diffusion were seen depending on the initial framework structure or the choice of frameworkmore » force field parameters. When framework flexibility effects were included, argon and krypton diffusion increased significantly compared to rigid-framework simulations using general force field parameters. Additionally, for argon and krypton in ZIF-8, guest diffusion increased with loading, demonstrating that guest-guest interactions between cages enhance inter-cage diffusion. No inter-cage jump events were seen for xenon atoms in ZIF-8 regardless of force field or initial structure, and the loading dependence of xenon diffusion in HKUST-1 is different for rigid and flexible frameworks. Diffusion of krypton and xenon in HKUST-1 depends on two competing effects: the steric effect that decreases diffusion as loading increases, and the “small cage effect” that increases diffusion as loading increases. Finally, a detailed analysis of the window size in ZIF-8 reveals that the window increases beyond its normal size to permit passage of a (nominally) larger krypton atom.« less

  15. Fabrication and characterization of inverted organic solar cells using shuttle cock-type metal phthalocyanine and PCBM:P3HT

    SciTech Connect (OSTI)

    Suzuki, Atsushi Furukawa, Ryo Akiyama, Tsuyoshi Oku, Takeo

    2015-02-27

    Inverted organic solar cells using shuttle cock-type phthalocyanine, semiconducting polymer and fullerenes were fabricated and characterized. Photovoltaic and optical properties of the solar cells with inverted structures were investigated by optical absorption, current density-voltage characteristics. The photovoltaic properties of the tandem organic solar cell using titanyl phthalocyanine, vanadyl phthalocyanine, poly(3-hexylthiophene) (P3HT) and [6, 6]-phenyl C{sub 61}-butyric acid methyl ester (PCBM) were improved. Effect of annealing and solvent treatment on surface morphologies of the active layer was investigated. The photovoltaic mechanisms, energy levels and band gap of active layers were discussed for improvement of the photovoltaic performance.

  16. Polymer-assisted aqueous deposition of metal oxide films (Patent...

    Office of Scientific and Technical Information (OSTI)

    Polymer-assisted aqueous deposition of metal oxide films Title: Polymer-assisted aqueous deposition of metal oxide films An organic solvent-free process for deposition of metal ...

  17. The Partnership Evaluation Framework

    Broader source: Energy.gov [DOE]

    U.S. Department of Energy Better Buildings Neighborhood Program: The Partnership Evaluation Framework: How to evaluate a potential partner’s business model and identify areas for collaboration.

  18. Generic Overlay Framework

    Energy Science and Technology Software Center (OSTI)

    2005-09-01

    This software provides a framework for building application layter overlay networks. It includes example overlays that can be used without modification. Also provided are example multicast and routing protocols that can be used with the overlays.

  19. A magnesium-carboxylate framework showing luminescent sensing for CS{sub 2} and nitroaromatic compounds

    SciTech Connect (OSTI)

    Wu, Zhao-Feng; Tan, Bin; Feng, Mei-Ling; Du, Cheng-Feng; Huang, Xiao-Ying

    2015-03-15

    A magnesium metal-organic framework compound, namely [NH{sub 2}(CH{sub 3}){sub 2}][Mg{sub 3}(NDC){sub 2.5}(HCO{sub 2}){sub 2}(DMF){sub 0.75}(H{sub 2}O){sub 0.25}]·1.25DMF·0.75H{sub 2}O (1) (H{sub 2}NDC=1,4-naphthalene dicarboxylic acid, DMF=N,N′-dimethylformamide), has been synthesized in solvothermal conditions and structurally characterized. It features a three-dimensionally anionic framework with aligned channels parallel to the b-axis. Luminescent studies indicated that it showed significant luminescence quenching for carbon disulfide (CS{sub 2}) and nitrobenzene after being activated, at a content of only 3.0 and 0.1 vol% in DMF, respectively. In addition, the activated sample showed sensitive luminescence quenching for 1,3,5-trinitrophenol with a low concentration of 5×10{sup −5} mol/L. - Graphical abstract: Presented is a microporous 3D Mg-MOF, namely, [NH{sub 2}(CH{sub 3}){sub 2}][Mg{sub 3}(NDC){sub 2.5}(HCO{sub 2}){sub 2}(DMF){sub 0.75}(H{sub 2}O){sub 0.25}]·1.25DMF·0.75H{sub 2}O (1) (H{sub 2}NDC=1,4-naphthalene dicarboxylic acid) showing significant luminescence quenching for carbon disulfide and nitrobenzene. - Highlights: • A microporous 3D metal-organic framework based on Mg. • The compound shows significant luminescence quenching for CS{sub 2} and nitrobenzene after activated. • The compound shows sensitive luminescence quenching for 1,3,5-trinitrophenol with a low concentration of 5×10{sup −5} mol/L.

  20. Metal decontamination for waste minimization using liquid metal refining technology

    SciTech Connect (OSTI)

    Joyce, E.L. Jr.; Lally, B.; Ozturk, B.; Fruehan, R.J.

    1993-09-01

    The current Department of Energy Mixed Waste Treatment Project flowsheet indicates that no conventional technology, other than surface decontamination, exists for metal processing. Current Department of Energy guidelines require retrievable storage of all metallic wastes containing transuranic elements above a certain concentration. This project is in support of the National Mixed Low Level Waste Treatment Program. Because of the high cost of disposal, it is important to develop an effective decontamination and volume reduction method for low-level contaminated metals. It is important to be able to decontaminate complex shapes where surfaces are hidden or inaccessible to surface decontamination processes and destruction of organic contamination. These goals can be achieved by adapting commercial metal refining processes to handle radioactive and organic contaminated metal. The radioactive components are concentrated in the slag, which is subsequently vitrified; hazardous organics are destroyed by the intense heat of the bath. The metal, after having been melted and purified, could be recycled for use within the DOE complex. In this project, we evaluated current state-of-the-art technologies for metal refining, with special reference to the removal of radioactive contaminants and the destruction of hazardous organics. This evaluation was based on literature reports, industrial experience, plant visits, thermodynamic calculations, and engineering aspects of the various processes. The key issues addressed included radioactive partitioning between the metal and slag phases, minimization of secondary wastes, operability of the process subject to widely varying feed chemistry, and the ability to seal the candidate process to prevent the release of hazardous species.

  1. Determining thermochemical properties of halogenated metals:...

    Office of Scientific and Technical Information (OSTI)

    metals: On enabling the rapid assessment of agent defeat formulations You ... Country of Publication: United States Language: English Subject: 37 INORGANIC, ORGANIC, ...

  2. Human choice and climate change. Volume 1: The societal framework

    SciTech Connect (OSTI)

    Rayner, S.; Malone, E.L.

    1997-12-31

    Foreward: Preface; Introduction; Science and decisionmaking; Population and climate change; Human needs and wants; Cultural discourses; Institutional frameworks for political action; and Sponsoring organizations, International Advisory Board, and project participants.

  3. Electronic structure of metallic glasses

    SciTech Connect (OSTI)

    Oelhafen, P.; Lapka, R.; Gubler, U.; Krieg, J.; DasGupta, A.; Guentherodt, H.J.; Mizoguchi, T.; Hague, C.; Kuebler, J.; Nagel, S.R.

    1981-01-01

    This paper is organized in six sections and deals with (1) the glassy transition metal alloys, their d-band structure, the d-band shifts on alloying and their relation to the alloy heat of formation (..delta..H) and the glass forming ability, (2) the glass to crystal phase transition viewed by valence band spectroscopy, (3) band structure calculations, (4) metallic glasses prepared by laser glazing, (5) glassy normal metal alloys, and (6) glassy hydrides.

  4. Unexpected bismuth concentration profiles in metal-organic vapor phase epitaxy-grown Ga(As{sub 1−x}Bi{sub x})/GaAs superlattices revealed by Z-contrast scanning transmission electron microscopy imaging

    SciTech Connect (OSTI)

    Wood, A. W.; Babcock, S. E.; Guan, Y.; Forghani, K.; Anand, A.; Kuech, T. F.

    2015-03-01

    A set of GaAs{sub 1−x}Bi{sub x}/GaAs multilayer quantum-well structures was deposited by metal-organic vapor phase epitaxy at 390 °C and 420 °C. The precursor fluxes were introduced with the intent of growing discrete and compositionally uniform GaAs{sub 1−x}Bi{sub x} well and GaAs barrier layers in the epitaxial films. High-resolution high-angle annular-dark-field (or “Z-contrast”) scanning transmission electron microscopy imaging revealed concentration profiles that were periodic in the growth direction, but far more complicated in shape than the intended square wave. The observed composition profiles could explain various reports of physical properties measurements that suggest compositional inhomogeneity in GaAs{sub 1−x}Bi{sub x} alloys as they currently are grown.

  5. Bivalent metal-based MIL-53 analogues: Synthesis, properties and application

    SciTech Connect (OSTI)

    Liu, Yongxin; Liu, Dan; Wang, Cheng

    2015-03-15

    Trivalent metal-based MIL-53 (Al{sup 3+}, Cr{sup 3+}, Fe{sup 3+}, In{sup 3+}) compounds are interesting metal–organic frameworks (MOFs) with breathing effect and are promising gas sorption materials. Replacing bridging μ{sub 2}-OH group by neutral ligands such as pyridine N-oxide and its derivatives (PNOs), the trivalent metal-based MIL-53 analogous structures could be extended to bivalent metal systems. The introduction of PNOs and bivalent metal elements endows the frameworks with new structural features and physical and chemical properties. This minireview summarizes the recent development of bivalent metal-based MIL-53 analogues (Mn{sup 2+}, Co{sup 2+}, Ni{sup 2+}), typically, focusing on the synthetic strategies and potential applications based on our own works and literatures. We present the synthetic strategy to achieve structures evolution from single-ligand-walled to double-ligand-walled channel. Properties and application of these new materials in a wide range of potential areas are discussed including thermal stability, gas adsorption, magnetism and liquid-phase separation. Promising directions of this research field are also highlighted. - Graphical abstract: The recent development of bivalent metal-based MIL-53 analogues (Mn{sup 2+}, Co{sup 2+}, Ni{sup 2+}) on their synthetic strategies, properties and potential applications was reviewed. - Highlights: • Structure features of bivalent metal-based MIL-53 analogues are illustrated. • Important properties and application are presented. • Host–guest interactions are main impetus for liquid-phase separation. • Promising directions of bivalent metal-based MIL-53 analogues are highlighted.

  6. Synthesis of framework isomer MOFs containing zinc and 4-tetrazolyl benzenecarboxylic acid via a structure directing solvothermal approach

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Ordonez, Carlos; Kinnibrugh, Tiffany L.; Xu, Hongwu; Lindline, Jennifer; Timofeeva, Tatiana; Wei, Qiang

    2015-04-02

    The solvothermal synthesis of framework isomers was carried out using the hybrid carboxylate and tetrazolate functional ligand, 4-tetrazolyl benzenecarboxylic acid (H₂TBC, TBC = 4-tetrazolyl benzenecarboxylate) and zinc. H₂TBC was also synthesized with the solvothermal approach, and is referred herein as structure 1. Using single-crystal X-ray diffraction, we found that the tetrazolate groups of TBC show an unusual “opposite-on” coordination mode with zinc. Three previously characterized metal-organic frameworks (MOFs) were obtained by systematically changing the solvents of the H₂TBC-Zn reaction, (1) ZnTBC, 2, which has a non-porous structure; (2) Zn₂(TBC)₂(H2O), 3, which has an amphiphilic pore structure and (3) Zn₂(TBC)₂{guest}, 4,more » which is porous and has channels containing uncoordinated N heteroatoms. Fluorescence spectra of 4 reveal a strong blue emission mainly from the TBC ligands.« less

  7. Synthesis of framework isomer MOFs containing zinc and 4-tetrazolyl benzenecarboxylic acid via a structure directing solvothermal approach

    SciTech Connect (OSTI)

    Ordonez, Carlos; Kinnibrugh, Tiffany L.; Xu, Hongwu; Lindline, Jennifer; Timofeeva, Tatiana; Wei, Qiang

    2015-04-02

    The solvothermal synthesis of framework isomers was carried out using the hybrid carboxylate and tetrazolate functional ligand, 4-tetrazolyl benzenecarboxylic acid (H₂TBC, TBC = 4-tetrazolyl benzenecarboxylate) and zinc. H₂TBC was also synthesized with the solvothermal approach, and is referred herein as structure 1. Using single-crystal X-ray diffraction, we found that the tetrazolate groups of TBC show an unusual “opposite-on” coordination mode with zinc. Three previously characterized metal-organic frameworks (MOFs) were obtained by systematically changing the solvents of the H₂TBC-Zn reaction, (1) ZnTBC, 2, which has a non-porous structure; (2) Zn₂(TBC)₂(H2O), 3, which has an amphiphilic pore structure and (3) Zn₂(TBC)₂{guest}, 4, which is porous and has channels containing uncoordinated N heteroatoms. Fluorescence spectra of 4 reveal a strong blue emission mainly from the TBC ligands.

  8. METAL PHTHALOCYANINES

    DOE Patents [OSTI]

    Frigerio, N.A.

    1962-03-27

    A process is given for preparing heavy metal phthalocyanines, sulfonated or not. The process comprises mixing an inorganic metal salt with dimethyl formamide or methyl sulfoxide; separating the metal complex formed from the solution; mixing the complex with an equimolar amount of sodium, potassium, lithium, magnesium, or beryllium sulfonated or unsulfonated phthalocyanine whereby heavy-metal phthalocyanine crystals are formed; and separating the crystals from the solution. Uranyl, thorium, lead, hafnium, and lanthanide rare earth phthalocyanines can be produced by the process. (AEC)

  9. Silicone metalization

    DOE Patents [OSTI]

    Maghribi, Mariam N.; Krulevitch, Peter; Hamilton, Julie

    2006-12-05

    A system for providing metal features on silicone comprising providing a silicone layer on a matrix and providing a metal layer on the silicone layer. An electronic apparatus can be produced by the system. The electronic apparatus comprises a silicone body and metal features on the silicone body that provide an electronic device.

  10. Silicone metalization

    DOE Patents [OSTI]

    Maghribi, Mariam N.; Krulevitch, Peter; Hamilton, Julie

    2008-12-09

    A system for providing metal features on silicone comprising providing a silicone layer on a matrix and providing a metal layer on the silicone layer. An electronic apparatus can be produced by the system. The electronic apparatus comprises a silicone body and metal features on the silicone body that provide an electronic device.

  11. Hypercrosslinked phenolic polymers with well developed mesoporous frameworks

    SciTech Connect (OSTI)

    Zhang, Jinshui; Qiao, Zhenan -An; Mahurin, Shannon Mark; Jiang, Xueguang; Chai, Song -Hai; Lu, Hanfeng; Nelson, Kimberly M.; Dai, Sheng

    2015-02-12

    A soft chemistry synthetic strategy based on a Friedel Crafts alkylation reaction is developed for the textural engineering of phenolic resin (PR) with a robust mesoporous framework to avoid serious framework shrinkage and maximize retention of organic functional moieties. By taking advantage of the structural benefits of molecular bridges, the resultant sample maintains a bimodal micro-mesoporous architecture with well-preserved organic functional groups, which is effective for carbon capture. Furthermore, this soft chemistry synthetic protocol can be further extended to nanotexture other aromatic-based polymers with robust frameworks.

  12. Hypercrosslinked Phenolic Polymers with Well Developed Mesoporous Frameworks

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Mahurin, Shannon Mark; Dai, Sheng

    2015-01-01

    A soft chemistry synthetic strategy based on a Friedel Crafts alkylation reaction is developed for the textural engineering of phenolic resin (PR) with a robust mesoporous framework to avoid serious framework shrinkage and maximize retention of organic functional moieties. By taking advantage of the structural benefits of molecular bridges, the resultant sample maintains a bimodal micro-mesoporous architecture with well-preserved organic functional groups, which is effective for carbon capture. Moreover, this soft chemistry synthetic protocol can be further extended to nanotexture other aromatic-based polymers with robust frameworks.

  13. Sci-Vis Framework

    Energy Science and Technology Software Center (OSTI)

    2015-03-11

    SVF is a full featured OpenGL 3d framework that allows for rapid creation of complex visualizations. The SVF framework handles much of the lifecycle and complex tasks required for a 3d visualization. Unlike a game framework SVF was designed to use fewer resources, work well in a windowed environment, and only render when necessary. The scene also takes advantage of multiple threads to free up the UI thread as much as possible. Shapes (actors) inmore » the scene are created by adding or removing functionality (through support objects) during runtime. This allows a highly flexible and dynamic means of creating highly complex actors without the code complexity (it also helps overcome the lack of multiple inheritance in Java.) All classes are highly customizable and there are abstract classes which are intended to be subclassed to allow a developer to create more complex and highly performant actors. There are multiple demos included in the framework to help the developer get started and shows off nearly all of the functionality. Some simple shapes (actors) are already created for you such as text, bordered text, radial text, text area, complex paths, NURBS paths, cube, disk, grid, plane, geometric shapes, and volumetric area. It also comes with various camera types for viewing that can be dragged, zoomed, and rotated. Picking or selecting items in the scene can be accomplished in various ways depending on your needs (raycasting or color picking.) The framework currently has functionality for tooltips, animation, actor pools, color gradients, 2d physics, text, 1d/2d/3d textures, children, blending, clipping planes, view frustum culling, custom shaders, and custom actor states« less

  14. Solid-state chemistry of molecular metal oxide clusters. Multiple, sequential C-H activation processes in the hydrogenation of coordinated cyclooctene. Lattice mobility of small organic molecules

    SciTech Connect (OSTI)

    Siedle, A.R.; Newmark, R.A.; Sahyun, M.R.V.; Lyon, P.A.; Hunt, S.L.; Skarjune, R.P. )

    1989-10-25

    Reaction of solid ((Ph{sub 3}P){sub 2}Ir(C{sub 8}H{sub 12})){sub 3}PW{sub 12}O{sub 40} with D{sub 2} gas produces cyclooctane containing up to 16 deuterium atoms. The c-C{sub 8}D{sub n}H{sub 16-n} isotopomer distribution is analyzed by Poisson statistics and interpreted in terms of C-H activation involving Ir-D-C-H exchange in an intermediate species containing coordinated cyclooctene. The results are compared with those from D{sub 2} reduction of ((Ph{sub 3}P){sub 2}Ir(C{sub 8}H{sub 12}))(PF{sub 6}) in the solid state and in acetone solution, in which cases, an additional exchange process operates. Solid-state {sup 2}H NMR shows that, even at low temperatures, small organic molecules such as cyclooctane and benzene undergo nearly isotropic motion.

  15. Sorption of colloids, organics, and metals onto gas-water interfaces: Transport mechanisms and potential remediation technology. 1998 annual progress report

    SciTech Connect (OSTI)

    Wan, J.; Tokunaga, T.K.

    1998-06-01

    'Although contaminant sorption at mineral surfaces has received much recognition as a major mechanism controlling contaminant behavior in subsurface environments, virtually no attention has been given to the possibility of contaminant sorption at gas-water interfaces. Moreover, no effort has yet been advanced to optimize such interactions for the purpose of facilitating in-situ remediation. Gas-water interfaces, unlike water-solid interfaces, are mobile. Therefore, associations of contaminants with gas-water interfaces can be very important not only in subsurface contaminant distributions, but also in contaminant transport, and potentially in remediation. The first objective of this research is to develop a quantitative understanding of interactions between contaminants and gas-water interfaces. The anticipated results will provide insights into the poorly understood phenomenon of contaminant interactions with the gas-water interface, and improve the current conceptual models of contaminant behavior in subsurface environments. The second purpose of this research is to explore the possibility of using surfactant stabilized microbubbles for in-situ remediation. Both pump-and-treat, and air sparging remediation methods are ineffective at displacing contaminants in zones which are advectively inaccessible. Stable microbubbles can migrate beyond preferential flow pathways and enter lower permeability zones by buoyant rise. The microbubbles can deliver oxygen and nutrients for promoting aerobic degradation of organic contaminants, and also deliver surfactants for emulsifying NAPLs.'

  16. EMN Framework Examples

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    EMN Framework Examples Palo Alto, CA April 15, 2016 Neha Rustagi Technology Manager Fuel Cell Technologies Office | 2 New Material Innovations for Clean Energy 2X Faster and 2X Cheaper Predictive Simulation Across Scales Synthesis & Characterization Rapid Screening End Use Performance Process Scalability Process Control Real-time Characterization Reliability Validation Data Management & Informatics Coordinated resource network with a suite of capabilities for advanced materials R&D

  17. Nuclear Safety Regulatory Framework

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Department of Energy Nuclear Safety Regulatory Framework DOE's Nuclear Safety Enabling Legislation Regulatory Enforcement & Oversight Regulatory Governance Atomic Energy Act 1946 Atomic Energy Act 1954 Energy Reorganization Act 1974 DOE Act 1977 Authority and responsibility to regulate nuclear safety at DOE facilities 10 CFR 830 10 CFR 835 10 CFR 820 Regulatory Implementation Nuclear Safety Radiological Safety Procedural Rules ISMS-QA; Operating Experience; Metrics and Analysis Cross Cutting

  18. Enhanced O-2 Selectivity versus N-2 by Partial Metal Substitution in Cu-BTC

    SciTech Connect (OSTI)

    Sava Gallis, Dorina F.; Parkes, Marie V.; Greathouse, Jeffery A.; Zhang, Xiaoyi; Nenoff, Tina M.

    2015-03-24

    Here, we describe the homogeneous substitution of Mn, Fe, and Co at various levels into a prototypical metal organic framework (MOP), namely Cu-BTC (HKUST-1), and the effect of that substitution on preferential gas sorption. Using a combination of density functional theory (DFT) calculations, postsynthetic metal substitutions, materials characterization, and gas sorption testing, we demonstrate that the identity of the metal ion has a quantifiable effect on their oxygen and nitrogen sorption properties at cryogenic temperatures. An excellent correlation is found between O-2/N-2 selectivities determined experimentally at 77 K and the difference in O-2 and N-2 binding energies calculated from DFT modeling data: Mn > Fe Co >> Cu. Room temperature gas sorption studies were also performed and correlated with metal substitution. The Fe-exchanged sample shows a significantly higher nitrogen isosteric heat of adsorption at temperatures close to ambient conditions (273-298 K) as compared to all other metals studied, indicative of favorable interactions between N-2 and coordinatively unsaturated Fe metal centers. Interestingly, differences in gas adsorption results at cryogenic and room temperatures are evident; they are explained by comparing experimental results with DFT binding energies (0 K) and room temperature Grand Canonical Monte Carlo simulations.

  19. Enhanced O2 selectivity versus N2 by partial metal substitution in Cu-BTC

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Sava Gallis, Dorina F.; Parkes, Marie V.; Greathouse, Jeffery A.; Zhang, Xiaoyi; Nenoff, Tina M.

    2015-03-05

    Here we describe the homogeneous substitution of Mn, Fe and Co at various levels into a prototypical metal-organic framework (MOF), namely Cu-BTC (HKUST-1), and the effect of that substitution on preferential gas sorption. Using a combination of density functional theory (DFT) calculations, postsynthetic metal substitutions, materials characterization, and gas sorption testing, we demonstrate that the identity of the metal ion has a quantifiable effect on their oxygen and nitrogen sorption properties at cryogenic temperatures. An excellent correlation is found between O2/N2 selectivities determined experimentally at 77 K and the difference in O2 and N2 binding energies calculated from DFT modelingmore » data: Mn > Fe > Co > Cu. Room temperature gas sorption studies were also performed and correlated with metal substitution. The Fe-exchanged sample shows a significantly higher nitrogen isosteric heat of adsorption at temperatures close to ambient conditions (273 K - 298 K) as compared to all other metals studied, indicative of favorable interactions between N2 and coordinatively unsaturated Fe metal centers. Furthermore, differences in gas adsorption results at cryogenic and room temperatures are evident; they are explained by comparing experimental results with DFT binding energies (0 K) and room temperature Grand Canonical Monte Carlo simulations.« less

  20. Yangyang Liu | Center for Gas SeparationsRelevant to Clean Energy...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    EFRC research: My research focuses on the design and synthesis of metal-organic frameworks ... magnesium metal-organic framework constructed from infinite metal chains, Cryst. ...

  1. Synthesis, structure and photoluminescence properties of amine-templated open-framework bismuth sulfates

    SciTech Connect (OSTI)

    Marri, Subba R.; Behera, J.N.

    2014-02-15

    Two organically-templated bismuth sulfates of the compositions, [C{sub 6}N{sub 2}H{sub 14}] [Bi(SO{sub 4}){sub 2}(NO{sub 3})], (1) and [C{sub 4}N{sub 2}H{sub 12}]{sub 4}[Bi{sub 4}(SO{sub 4}){sub 10}(H{sub 2}O){sub 4}], (2), with open architecture have been synthesized and their structures determined by single crystal X-ray diffraction. 1 has a corrugated layered structure with 8-membered aperture wherein the SO{sub 4} tetrahedra and the BiO{sub 8} polyhedra join together to form (4, 4) net sheets of the metal centers while 2 has a three-dimensional structure possessing 8- and 12-membered channels. Both the compounds show good fluorescence properties exhibiting blue luminescence. Time-resolved fluorescence behavior of 1 and 2 shows mean fluorescence life time of 0.9 and 1.0 ns, respectively. - Graphical abstract: Two open-framework bismuth sulfates with the layered and three-dimensional structures have been synthesized and characterized. Both the compounds show good fluorescence properties exhibiting blue luminescence. Display Omitted - Highlights: Two organically-templated bismuth sulfates with open architecture have been synthesized and characterized. One has a corrugated layered structure while the other one has a three-dimensional structure possessing channels. They are novel in that open-framework three-dimensional main group metal sulfates are first to be reported. They show good fluorescence properties exhibiting blue luminescence.

  2. Robust Systems Test Framework

    Energy Science and Technology Software Center (OSTI)

    2003-01-01

    The Robust Systems Test Framework (RSTF) provides a means of specifying and running test programs on various computation platforms. RSTF provides a level of specification above standard scripting languages. During a set of runs, standard timing information is collected. The RSTF specification can also gather job-specific information, and can include ways to classify test outcomes. All results and scripts can be stored into and retrieved from an SQL database for later data analysis. RSTF alsomore » provides operations for managing the script and result files, and for compiling applications and gathering compilation information such as optimization flags.« less

  3. Spark Distributed Analytic Framework

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Apache Spark Spark Distributed Analytic Framework Description and Overview Apache Spark(tm) is a fast and general engine for large-scale data processing. How to Use Spark Because of its high memory and I/O bandwidth requirements, we recommend you run your spark jobs on Cori. Follow the steps below to use spark, note that the order of the commands matters. DO NOT load the spark module until you are inside a batch job. Interactive mode Submit an interactive batch job with at least 2 nodes: salloc

  4. Longitudinal spin Seebeck effect in Nd{sub 2}BiFe{sub 5−x}Ga{sub x}O{sub 12} prepared on gadolinium gallium garnet (001) by metal organic decomposition method

    SciTech Connect (OSTI)

    Asada, H. Kuwahara, A.; Sakata, N.; Ono, T.; Kishimoto, K.; Koyanagi, T.; Ishibashi, T.; Meguro, A.; Hashinaka, T.

    2015-05-07

    Nd{sub 2}BiFe{sub 5−x}Ga{sub x}O{sub 12} thin films with the Ga composition x = 0, 0.5, and 1.0 are prepared on (001) oriented gadolinium gallium garnet substrates by a metal organic decomposition method. Only (001) peaks are observed in x-ray diffraction patterns for all the films, suggesting that the highly oriented Nd{sub 2}BiFe{sub 5−x}Ga{sub x}O{sub 12} thin films were formed. Increasing Ga composition, the saturation magnetization decreases, and the perpendicular easy axis is enhanced due to the decrease of the shape anisotropy. Longitudinal spin Seebeck effects (LSSEs) in Nd{sub 2}BiFe{sub 5−x}Ga{sub x}O{sub 12} thin films with a Pt layer of 10 nm in thickness were investigated. Magnetic field dependence of the thermoelectric voltage caused by the LSSE in Nd{sub 2}BiFe{sub 5−x}Ga{sub x}O{sub 12} films indicates the hysteresis loop with the small coercivity reflecting the magnetization curve. The decrease of LSSE voltage in Nd{sub 2}BiFe{sub 5−x}Ga{sub x}O{sub 12} is clearly observed with the decrease of Fe composition.

  5. Metal oxide films on metal

    DOE Patents [OSTI]

    Wu, Xin D. (Los Alamos, NM); Tiwari, Prabhat (Los Alamos, NM)

    1995-01-01

    A structure including a thin film of a conductive alkaline earth metal oxide selected from the group consisting of strontium ruthenium trioxide, calcium ruthenium trioxide, barium ruthenium trioxide, lanthanum-strontium cobalt oxide or mixed alkaline earth ruthenium trioxides thereof upon a thin film of a noble metal such as platinum is provided.

  6. Heavy metal movement in metal-contaminated soil profiles

    SciTech Connect (OSTI)

    Li, Zhenbin; Shuman, L.M.

    1996-10-01

    Heavy metal movement in soil profiles is a major environmental concern because even slow transport through the soil may eventually lead to deterioration of groundwater quality. In this study, three metal-contaminated soil (Fuquay, Dothan, and Clarendon) were selected from cropland were a high-metal flue dust had been applied annually for 6 years to raise soil pH, with application ending 4 years before sampling. One uncontaminated soil (Tifton) from the same physiographic area was also sampled as a control. Soil samples were collected in 15-cm increments from the surface to 105 cm in depth. Total contents of Zn, Cd, and Pb in the soils samples were determined. To better understand metal movement in relation to metal fractions in the soil profile, soil samples were also extracted sequentially for exchangeable (EXC), organic matter (OM), Mn oxide (MNO), amorphous Fe oxide (AFEO), crystalline Fe oxide (CFEO), and residual (RES) fractions. 35 refs., 6 figs., 2 tabs.

  7. Metal Hydrides

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Metal Hydrides Theodore Motyka Savannah River National Laboratory Metal Hydride System Architect Jose-Miguel Pasini, & Bart van Hassel UTRC Claudio Corgnale & Bruce Hardy SRNL Kevin Simmons and Mark Weimar PNNL Darsh Kumar GM, Matthew Thornton NREL, Kevin Drost OSU DOE Materials-Based Hydrogen Storage Summit Defining Pathways for Onboard Automotive Applications 2 Outline * Background and MH History * MH HSECoE Results * Material Operating Requirements * Modeling and Analyses * BOP and

  8. Using the CMS threaded framework in a production environment

    SciTech Connect (OSTI)

    Jones, C. D.; Contreras, L.; Gartung, P.; Hufnagel, D.; Sexton-Kennedy, L.

    2015-12-23

    During 2014, the CMS Offline and Computing Organization completed the necessary changes to use the CMS threaded framework in the full production environment. We will briefly discuss the design of the CMS Threaded Framework, in particular how the design affects scaling performance. We will then cover the effort involved in getting both the CMSSW application software and the workflow management system ready for using multiple threads for production. Finally, we will present metrics on the performance of the application and workflow system as well as the difficulties which were uncovered. As a result, we will end with CMS' plans for using the threaded framework to do production for LHC Run 2.

  9. Dendritic metal nanostructures

    DOE Patents [OSTI]

    Shelnutt, John A.; Song, Yujiang; Pereira, Eulalia F.; Medforth, Craig J.

    2010-08-31

    Dendritic metal nanostructures made using a surfactant structure template, a metal salt, and electron donor species.

  10. Dispersed metal cluster catalysts by design. Synthesis, characterization, structure, and performance

    SciTech Connect (OSTI)

    Arslan, Ilke; Dixon, David A.; Gates, Bruce C.; Katz, Alexander

    2015-09-30

    To understand the class of metal cluster catalysts better and to lay a foundation for the prediction of properties leading to improved catalysts, we have synthesized metal catalysts with well-defined structures and varied the cluster structures and compositions systematically—including the ligands bonded to the metals. These ligands include supports and bulky organics that are being tuned to control both the electron transfer to or from the metal and the accessibility of reactants to influence catalytic properties. We have developed novel syntheses to prepare these well-defined catalysts with atomic-scale control the environment by choice and placement of ligands and applied state-of-the art spectroscopic, microscopic, and computational methods to determine their structures, reactivities, and catalytic properties. The ligands range from nearly flat MgO surfaces to enveloping zeolites to bulky calixarenes to provide controlled coverages of the metal clusters, while also enforcing unprecedented degrees of coordinative unsaturation at the metal site—thereby facilitating bonding and catalysis events at exposed metal atoms. With this wide range of ligand properties and our arsenal of characterization tools, we worked to achieve a deep, fundamental understanding of how to synthesize robust supported and ligand-modified metal clusters with controlled catalytic properties, thereby bridging the gap between active site structure and function in unsupported and supported metal catalysts. We used methods of organometallic and inorganic chemistry combined with surface chemistry for the precise synthesis of metal clusters and nanoparticles, characterizing them at various stages of preparation and under various conditions (including catalytic reaction conditions) and determining their structures and reactivities and how their catalytic properties depend on their compositions and structures. Key characterization methods included IR, NMR, and EXAFS spectroscopies to identify

  11. Energy Sector Cybersecurity Framework Implementation Guidance

    Broader source: Energy.gov (indexed) [DOE]

    FOR PUBLIC COMMENT SEPTEMBER, 2014 ENERGY SECTOR CYBERSECURITY FRAMEWORK IMPLEMENTATION GUIDANCE Energy Sector Cybersecurity Framework Implementation Guidance Table of Contents...

  12. Treatment of organic waste

    DOE Patents [OSTI]

    Grantham, LeRoy F.

    1979-01-01

    An organic waste containing at least one element selected from the group consisting of strontium, cesium, iodine and ruthenium is treated to achieve a substantial reduction in the volume of the waste and provide for fixation of the selected element in an inert salt. The method of treatment comprises introducing the organic waste and a source of oxygen into a molten salt bath maintained at an elevated temperature to produce solid and gaseous reaction products. The gaseous reaction products comprise carbon dioxide and water vapor, and the solid reaction products comprise the inorganic ash constituents of the organic waste and the selected element which is retained in the molten salt. The molten salt bath comprises one or more alkali metal carbonates, and may optionally include from 1 to about 25 wt.% of an alkali metal sulfate.

  13. Metal hydrides

    SciTech Connect (OSTI)

    Carnes, J.R.; Kherani, N.P.

    1987-11-01

    Metal hydride information is not available for most hydrides in a consolidated quick-reference source. This report's objective is to fill the need for such a document providing basic thermodynamic data for as many metal hydrides as possible. We conduced a computerized library search to access as many sources as possible and screened each source for such thermodynamic data as pressure-temperature graphs, van't Hoff curves, and impurity effects. We included any other relevant information and commented on it. A primary concern to be investigated in the future is the behavior of metal tritides. This would be important in the area of emergency tritium cleanup systems. The hydride graphs are useful, however, as tritides may be expected in most cases to behave similarly and at least follow trends of their respective hydrides. 42 refs., 40 figs., 5 tabs.

  14. Mercury(II) nitroprusside: A framework with an unusual topology

    SciTech Connect (OSTI)

    Cano, A.; Osiry, H.; Reguera, L.; Lemus-Santana, A.A.; Reguera, E.

    2015-05-15

    The titled compound was prepared by the precipitation method from diluted aqueous solution of sodium nitroprusside and mercury(II) nitrate. The orange solid formed, with formula unit Hg[Fe(CN){sub 5}NO], crystallizes with an orthorhombic unit cell in the Pmna space group with cell parameters: a=11.2788(3), b=6.1965(3), and c=12.3786(6) Å. The unit cell accommodates four formula of the compound (Z=4). Its crystal structure was solved from X-ray powder patterns and then refined by the Rietveld method. The material framework is formed by tetrahedral coordination of Hg atoms at the N end of the equatorial CN groups of the [Fe(CN){sub 5}NO] building block. That framework results from the interpenetration of two identical sub-frameworks with a relative shift of (a/2, b/2, c/2). The sub-framework has two types of cavities, ellipsoidal and rhombohedral, with transversal section of ca. 4.5×9.2 Å and ca. 8.5 Å transversal section, respectively. That system of cavities results eclipsed by the relative shift of neighboring sub-frameworks. No transport of H{sub 2} and N{sub 2} molecules through the material framework was observed. The thermal decomposition also reveals limitation for the decomposition products diffusion through the practically compact structure. The structural study was complemented with TG, IR, UV–vis and N{sub 2} and H{sub 2} adsorption data. Neighboring Hg atoms are distant 4.54(3) Å, a relatively large distance to suppose the existence of metal–metal interaction. No previous study on the crystal structure and related properties of mercury(II) nitroprusside has been reported. - Graphical abstract: Mercury(II) nitroprusside framework formed by two identical interpenetrated porous subframeworks where neighboring cavities appear eclipsed. - Highlights: • Interpenetrated frameworks in metal nitroprusside. • Eclipsed porous framework in metal nitroprusside. • Structure and related properties for mercury(II) nitroprusside. • Spectral features for

  15. A Physically Based Framework for Modelling the Organic Fractionation...

    Office of Scientific and Technical Information (OSTI)

    mixture with concentrations intermediate between lipids and polysaccharides, a processed mixture associated with recalcitrant surface DOC, and a deep abyssal humic-like mixture. ...

  16. Safe disposal of metal values in slag

    SciTech Connect (OSTI)

    Halpin, P.T.; Zarur, G.L.

    1982-10-26

    The method of safely disposing of sludge containing metal values capable of displaying toxic ecological properties includes the steps of deriving from an organic or inorganic sludge an intermediate product such as a dewatered sludge or an incinerated ash, and adding this intermediate product to a metal smelting step of a type producing a slag such that most of the metal values become encapsulated in the slag. Some precious metal values may be recovered with the metal being smelted, and may be subsequently separated therefrom by appropriate metal winning steps. The sludge product brings to the smelting process certain additives needed therein such as silica and phosphates for the slag, alumina and magnesium to lower the viscosity of the molten slag, and organic matter serving as reducing agents.

  17. METAL COMPOSITIONS

    DOE Patents [OSTI]

    Seybolt, A.U.

    1959-02-01

    Alloys of uranium which are strong, hard, and machinable are presented, These alloys of uranium contain bctween 0.1 to 5.0% by weight of at least one noble metal such as rhodium, palladium, and gold. The alloys may be heat treated to obtain a product with iniproved tensile and compression strengths,

  18. Mobility of Source Zone Heavy Metals and Radionuclides: The Mixed...

    Office of Scientific and Technical Information (OSTI)

    Various U. S. Department of Energy (DOE) low and medium-level radioactive waste sites contain mixtures of heavy metals, radionuclides and assorted organic materials. Over time, ...

  19. Metagenomic Insights into Evolution of a Heavy Metal-Contaminated...

    Office of Scientific and Technical Information (OSTI)

    exposure to high concentrations of heavy metals, nitric acid and organic solvents (;;50 ... metagenomics; microbial ecology; bioremediation Word Cloud More Like This Full Text ...

  20. Geochemical Impacts of Carbon Dioxide, Brine, Trace Metal and...

    Office of Scientific and Technical Information (OSTI)

    Carbon Dioxide, Brine, Trace Metal and Organic Leakage into an Unconfined, Oxidizing Limestone Aquifer Citation Details In-Document Search Title: Geochemical Impacts of Carbon ...

  1. Understanding Metal Directed-Assembly Growth of Single-Crystal...

    Office of Scientific and Technical Information (OSTI)

    The deterministic growth of oriented crystalline organic nanowires (CONs) from the vapor-solid chemical reaction (VSCR) between small-molecule reactants and metal nanoparticles has ...

  2. Knowledge Framework Implementation with Multiple Architectures - 13090

    SciTech Connect (OSTI)

    Upadhyay, H.; Lagos, L.; Quintero, W.; Shoffner, P.; DeGregory, J.

    2013-07-01

    Multiple kinds of knowledge management systems are operational in public and private enterprises, large and small organizations with a variety of business models that make the design, implementation and operation of integrated knowledge systems very difficult. In recent days, there has been a sweeping advancement in the information technology area, leading to the development of sophisticated frameworks and architectures. These platforms need to be used for the development of integrated knowledge management systems which provides a common platform for sharing knowledge across the enterprise, thereby reducing the operational inefficiencies and delivering cost savings. This paper discusses the knowledge framework and architecture that can be used for the system development and its application to real life need of nuclear industry. A case study of deactivation and decommissioning (D and D) is discussed with the Knowledge Management Information Tool platform and framework. D and D work is a high priority activity across the Department of Energy (DOE) complex. Subject matter specialists (SMS) associated with DOE sites, the Energy Facility Contractors Group (EFCOG) and the D and D community have gained extensive knowledge and experience over the years in the cleanup of the legacy waste from the Manhattan Project. To prevent the D and D knowledge and expertise from being lost over time from the evolving and aging workforce, DOE and the Applied Research Center (ARC) at Florida International University (FIU) proposed to capture and maintain this valuable information in a universally available and easily usable system. (authors)

  3. Organized for safety

    SciTech Connect (OSTI)

    McCleary, M.D.; Schuberth, P.C.; Hining, D.E.

    1996-11-01

    The Exxon Company, International Drilling Organization (ECIDO) is committed to an injury-free workplace through continuous efforts by identifying and eliminating or managing safety risks associated with drilling activities. The newly developed and recently completed ECIDO Safety Management Program (SMP) strengthens this commitment by defining a comprehensive, management approved, organized framework for drill teams from which operations safety is managed both effectively and consistently worldwide. The SMP is proactive, focuses on positive recognition, promotes greater individual involvement, and gives part ownership of the safety program at the rig level to the crews.

  4. Composite metal membrane

    DOE Patents [OSTI]

    Peachey, Nathaniel M.; Dye, Robert C.; Snow, Ronny C.; Birdsell, Stephan A.

    1998-01-01

    A composite metal membrane including a first metal layer of Group IVB met or Group VB metals, the first metal layer sandwiched between two layers of an oriented metal of palladium, platinum or alloys thereof is provided together with a process for the recovery of hydrogen from a gaseous mixture including contacting a hydrogen-containing gaseous mixture with a first side of a nonporous composite metal membrane including a first metal of Group IVB metals or Group VB metals, the first metal layer sandwiched between two layers of an oriented metal of palladium, platinum or alloys thereof, and, separating hydrogen from a second side of the nonporous composite metal membrane.

  5. Composite metal membrane

    DOE Patents [OSTI]

    Peachey, N.M.; Dye, R.C.; Snow, R.C.; Birdsell, S.A.

    1998-04-14

    A composite metal membrane including a first metal layer of Group IVB met or Group VB metals, the first metal layer sandwiched between two layers of an oriented metal of palladium, platinum or alloys thereof is provided together with a process for the recovery of hydrogen from a gaseous mixture including contacting a hydrogen-containing gaseous mixture with a first side of a nonporous composite metal membrane including a first metal of Group IVB metals or Group VB metals, the first metal layer sandwiched between two layers of an oriented metal of palladium, platinum or alloys thereof, and, separating hydrogen from a second side of the nonporous composite metal membrane.

  6. Nanoheterostructure Cation Exchange: Anionic Framework Conservation

    SciTech Connect (OSTI)

    Jain, Prashant K.; Amirav, Lilac; Aloni, Shaul; Alivisatos, A. Paul

    2010-05-11

    In ionic nanocrystals the cationic sub-lattice can be replaced with a different metal ion via a fast, simple, and reversible place-exchange, allowing post-synthetic modification of the composition of the nanocrystal, while preserving its size and shape. Here, we demonstrate for the first time that during such an exchange, the anionic framework of the crystal is preserved. When applied to nanoheterostructures, this phenomenon ensures that compositional interfaces within the heterostructure are conserved throughout the transformation. For instance, a morphology composed of a CdSe nanocrystal embedded in a CdS rod (CdSe/CdS) was exchanged to a PbSe/PbS nanorod via a Cu2Se/Cu2S structure. During every exchange cycle, the seed size and position within the nanorod were preserved, as evident by excitonic features, Z-contrast imaging, and elemental line-scans. Anionic framework conservation extends the domain of cation exchange to the design of more complex and unique nanostructures.

  7. Framework for Address Cooperative Extended Transactions

    Energy Science and Technology Software Center (OSTI)

    1997-12-01

    The Framework for Addressing Cooperative Extended Transactions (FACET) is an object-oriented software framework for building models of complex, cooperative behaviors of agents. it can be used to implement simulation models of societal processes such as the complex interplay of participating individuals and organizations engaged in multiple concurrent transactions in pursuit of their various goals. These transactions can be patterned on, for example, clinical guidelines and procedures, business practices, government and corporate policies, etc. FACET canmore » also address other complex behaviors such as biological life cycles or manufacturing processes. FACET includes generic software objects representing the fundamental classes of agent -- Person and Organization - with mechanisms for resource management, including resolution of conflicting requests for participation and/or use of the agent's resources. The FACET infrastructure supports stochastic behavioral elements and coping mechanisms by which specified special conditions and events can cause an active cooperative process to be preempted, diverting the participants onto appropriate alternative behavioral pathways.« less

  8. Zeolitic imidazolate frameworks for kinetic separation of propane and propene

    SciTech Connect (OSTI)

    Li, Jing; Li, Kunhao; Olson, David H.

    2014-08-05

    Zeolitic Imidazolate Frameworks (ZIFs) characterized by organic ligands consisting of imidazole ligands that are either essentially all 2-chloroimidazole ligands or essentially all 2-bromoimidazole ligands are disclosed. Methods for separating propane and propene with the ZIFs of the present invention, as well as other ZIFs, are also disclosed.

  9. 2016-2020 Strategic Plan and Implementing Framework

    SciTech Connect (OSTI)

    2015-11-01

    The 2016-2020 Strategic Plan and Implementing Framework from the Office of Energy Efficiency and Renewable Energy (EERE) is the blueprint for launching the nation’s leadership in the global clean energy economy. This document will guide the organization to build on decades of progress in powering our nation from clean, affordable and secure energy.

  10. Vitrification of organics-containing wastes

    DOE Patents [OSTI]

    Bickford, D.F.

    1995-01-01

    A process for stabilizing organics-containing waste materials and recovery metals therefrom, and a waste glass product made according to the process are described. Vitrification of wastes such as organic ion exchange resins, electronic components and the like can be accomplished by mixing at least one transition metal oxide with the wastes, and, if needed, glass formers to compensate for a shortage of silicates or other glass formers in the wastes. The transition metal oxide increases the rate of oxidation of organic materials in the wastes to improve the composition of the glass-forming mixture: at low temperatures, the oxide catalyzes oxidation of a portion of the organics in the waste; at higher temperatures, the oxide dissolves and the resulting oxygen ions oxidize more of the organics; and at vitrification temperatures, the metal ions conduct oxygen into the melt to oxidize the remaining organics. In addition, the transition metal oxide buffers the redox potential of the glass melt so that metals such as Au, Pt, Ag, and Cu separate form the melt in the metallic state and can be recovered. After the metals are recovered, the remainder of the melt is allowed to cool and may subsequently be disposed of. The product has good leaching resistance and can be disposed of in an ordinary landfill, or, alternatively, used as a filler in materials such as concrete, asphalt, brick and tile.

  11. Vitrification of organics-containing wastes

    DOE Patents [OSTI]

    Bickford, Dennis F.

    1997-01-01

    A process for stabilizing organics-containing waste materials and recovering metals therefrom, and a waste glass product made according to the process. Vitrification of wastes such as organic ion exchange resins, electronic components and the like can be accomplished by mixing at least one transition metal oxide with the wastes, and, if needed, glass formers to compensate for a shortage of silicates or other glass formers in the wastes. The transition metal oxide increases the rate of oxidation of organic materials in the wastes to improve the composition of the glass-forming mixture: at low temperatures, the oxide catalyzes oxidation of a portion of the organics in the waste; at higher temperatures, the oxide dissolves and the resulting oxygen ions oxidize more of the organics; and at vitrification temperatures, the metal ions conduct oxygen into the melt to oxidize the remaining organics. In addition, the transition metal oxide buffers the redox potential of the glass melt so that metals such as Au, Pt, Ag, and Cu separate from the melt in the metallic state and can be recovered. After the metals are recovered, the remainder of the melt is allowed to cool and may subsequently be disposed of. The product has good leaching resistance and can be disposed of in an ordinary landfill, or, alternatively, used as a filler in materials such as concrete, asphalt, brick and tile.

  12. Vitrification of organics-containing wastes

    DOE Patents [OSTI]

    Bickford, D.F.

    1997-09-02

    A process is described for stabilizing organics-containing waste materials and recovering metals therefrom, and a waste glass product made according to the process is also disclosed. Vitrification of wastes such as organic ion exchange resins, electronic components and the like can be accomplished by mixing at least one transition metal oxide with the wastes, and, if needed, glass formers to compensate for a shortage of silicates or other glass formers in the wastes. The transition metal oxide increases the rate of oxidation of organic materials in the wastes to improve the composition of the glass-forming mixture: at low temperatures, the oxide catalyzes oxidation of a portion of the organics in the waste; at higher temperatures, the oxide dissolves and the resulting oxygen ions oxidize more of the organics; and at vitrification temperatures, the metal ions conduct oxygen into the melt to oxidize the remaining organics. In addition, the transition metal oxide buffers the redox potential of the glass melt so that metals such as Au, Pt, Ag, and Cu separate from the melt in the metallic state and can be recovered. After the metals are recovered, the remainder of the melt is allowed to cool and may subsequently be disposed of. The product has good leaching resistance and can be disposed of in an ordinary landfill, or, alternatively, used as a filler in materials such as concrete, asphalt, brick and tile. 1 fig.

  13. Sample Business Plan Framework 5

    Broader source: Energy.gov [DOE]

    U.S. Department of Energy Better Buildings Neighborhood Program: Sample Business Plan Framework 5: A program that establishes itself as a government entity, then operates using a fee-based structure.

  14. Sample Business Plan Framework 2

    Broader source: Energy.gov [DOE]

    U.S. Department of Energy Better Buildings Neighborhood Program: Sample Business Plan Framework 1: A program seeking to continue operations in the post-grant period as a not-for-profit (NGO) entity.

  15. Sample Business Plan Framework 4

    Broader source: Energy.gov [DOE]

    U.S. Department of Energy Better Buildings Neighborhood Program: Sample Business Plan Framework 4: A program seeking to continue in the post-grant period as a marketing contractor to a utility.

  16. Sample Business Plan Framework 3

    Broader source: Energy.gov [DOE]

    U.S. Department of Energy Better Buildings Neighborhood Program: Sample Business Plan Framework 3: A government entity running a Commercial PACE program in the post-grant period.

  17. Sequentially Executed Model Evaluation Framework

    SciTech Connect (OSTI)

    2014-02-14

    Provides a message passing framework between generic input, model and output drivers, and specifies an API for developing such drivers. Also provides batch and real-time controllers which step the model and 1/0 through the time domain (or other discrete domain), and sample 1/0 drivers. This is a Framework library framework, and does not, itself, solve any problems or execute any modelling. The SeMe framework aids in development of models which operate on sequential information, such as time-series, where evaluation is based on prior results combined with new data for this iteration. Ha) applications in quality monitoring, and was developed as part of the CANARY-EDS software, where real-time water quality data is being analyzed

  18. Sequentially Executed Model Evaluation Framework

    Energy Science and Technology Software Center (OSTI)

    2014-02-14

    Provides a message passing framework between generic input, model and output drivers, and specifies an API for developing such drivers. Also provides batch and real-time controllers which step the model and 1/0 through the time domain (or other discrete domain), and sample 1/0 drivers. This is a Framework library framework, and does not, itself, solve any problems or execute any modelling. The SeMe framework aids in development of models which operate on sequential information, suchmore » as time-series, where evaluation is based on prior results combined with new data for this iteration. Ha) applications in quality monitoring, and was developed as part of the CANARY-EDS software, where real-time water quality data is being analyzed« less

  19. Sample Business Plan Framework 1

    Broader source: Energy.gov [DOE]

    U.S. Department of Energy Better Buildings Neighborhood Program: Sample Business Plan Framework 1: A program seeking to continue operations in the post-grant period as a not-for-profit (NGO) entity.

  20. METAL EXTRACTION PROCESS

    DOE Patents [OSTI]

    Lewis, G.W. Jr.; Rhodes, D.E.

    1957-11-01

    An improved method for extracting uranium from aqueous solutions by solvent extraction is presented. A difficulty encountered in solvent extraction operations using an organic extractant (e.g., tributyl phosphate dissolved in kerosene or carbon tetrachloride) is that emulsions sometimes form, and phase separation is difficult or impossible. This difficulty is overcome by dissolving the organic extractant in a molten wax which is a solid at operating temperatures. After cooling, the wax which now contains the extractant, is broken into small particles (preferably flakes) and this wax complex'' is used to contact the uranium bearing solutions and extract the metal therefrom. Microcrystalline petroleum wax and certain ethylene polymers have been found suitable for this purpose.