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. 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)....

  16. 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 ...

  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. 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....

  14. 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,...

  15. 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....

  16. 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....

  17. 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 ...

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

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    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; ...

  19. 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. ...

  20. 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, ...

  1. 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. ...

  2. 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; ...

  3. 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 ...

  4. 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. ...

  5. 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;...

  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. 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...

  9. 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 ; ...

  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. 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

  14. 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,"

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

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    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,...

  16. 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 ...

  17. 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...

  18. 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...

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

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    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...

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

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    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:...

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

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    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....

  2. 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...

  3. 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...

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

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    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 ...

  5. 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. ...

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

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    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, ...

  7. 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, ...

  8. 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, ...

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

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

    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, ...

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

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

    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, ...

  11. "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...

  12. 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,...

  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. 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...

  9. 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 ...

  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. 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...

  20. 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...

  1. 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...

  2. 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. ...

  3. 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.

  4. 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.

  5. 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, ...

  6. 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.

  7. 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. ...

  8. 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.

  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. 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...

  16. 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.

  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. 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.

  16. 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.

  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. 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.

  8. 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.

  9. 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

  10. 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

  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. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  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. 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.

  8. 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.

  9. 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.

  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. 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.

  15. 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.

  16. 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.

  17. 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.

  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. 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.

  4. 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.

  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. 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....

  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. 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.

  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

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    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 ...

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