Are you using the right probe molecules for assessing the textural properties of metal–organic frameworks?

Islamoglu, Timur; Idrees, Karam B.; Son, Florencia A.; Chen, Zhijie; Lee, Seung-Joon; Li, Peng; Farha, Omar K.

doi:10.1039/d1ta08021k

Title: Are you using the right probe molecules for assessing the textural properties of metal–organic frameworks?

Journal Article · 12 December 2021 · Journal of Materials Chemistry. A

DOI: https://doi.org/10.1039/d1ta08021k · OSTI ID:1978843

^[1];

^[2];

^[2]; Lee, Seung-Joon ^[2];

^[3];

^[2]

Northwestern University, Evanston, IL (United States); OSTI
Northwestern University, Evanston, IL (United States)
Fudan University, Shanghai (China)

Textural properties—such as the surface area, pore size distribution, and pore volume—are at the forefront of characterization for porous materials. Therefore, it is essential to accurately and reproducibly report a material's textural properties as they could ultimately dictate its applicability. This work aims to provide insightful and comprehensive studies of textural properties for a set of metal–organic frameworks (MOFs), a class of porous materials, using various gases to equip researchers in the field with a helpful guide and reference. Here, we selected a series of nine MOFs with different surface areas, pore sizes, shapes, and chemical environments to represent a wide range of materials. We probed the textural properties of these MOFs using traditional and distinctive gases: N₂, Kr and O₂ at 77 K, Ar at 87 K, and CO₂ at 195 and 273 K. With regard to surface area, we discuss the validity and challenges associated with the current BET method, the importance of utilizing the Rouquerol et al. consistency criteria to ensure accuracy and reproducibility, and the recommended gas probes for certain materials. For pore size distribution, we discuss the efficacy of each probe for determining the pore sizes within a porous material relative to the calculated distribution from its crystal structure, the limitations of current computational kernels used to calculate pore size distributions, and the need for advanced kernels to envelope the diversity of porous materials. Finally, for pore volume, we discuss the use of the Gurvich rule to obtain the total pore volume in comparison with calculated values from crystal structures and its consistency as a metric for porous materials. Ultimately, we hope that this article will aid researchers in characterizing the textural properties of porous materials and encourage the development of new kernels capable of encompassing the complexity of MOFs and other porous materials.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Northwestern Univ., Evanston, IL (United States); Univ. of Minnesota, Minneapolis, MN (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE); US Army Research Office (ARO); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: EE0008816; FG02-08ER15967; SC0012702

OSTI ID:: 1978843

Alternate ID(s):: OSTI ID: 1835457

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 1 Vol. 10; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (72)

Algorithms and tools for high-throughput geometry-based analysis of crystalline porous materials Willems, Thomas F.; Rycroft, Chris H.; Kazi, Michaeel Microporous and Mesoporous Materials, Vol. 149, Issue 1 https://doi.org/10.1016/j.micromeso.2011.08.020	journal	February 2012
Functional Porous Coordination Polymers Kitagawa, Susumu; Kitaura, Ryo; Noro, Shin-ichiro Angewandte Chemie International Edition, Vol. 43, Issue 18, p. 2334-2375 https://doi.org/10.1002/anie.200300610	journal	April 2004
Coupling Structural and Adsorption Properties of Metal–Organic Frameworks: From Pore Size Distribution to Pore Type Distribution Dantas, Silvio; Neimark, Alexander V. ACS Applied Materials & Interfaces, Vol. 12, Issue 13 https://doi.org/10.1021/acsami.0c01682	journal	March 2020
Modern microscopy methods for the structural study of porous materials Anderson, Michael W.; Ohsuna, Tetsu; Sakamoto, Yasuhiro Chemical Communications, Issue 8 https://doi.org/10.1039/B313208K	journal	January 2004
Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage Eddaoudi, Mohamed; Kim, Jaheon; Rosi, Nathaniel Science, Vol. 295, Issue 5554, p. 469-472 https://doi.org/10.1126/science.1067208	journal	January 2002
Balancing volumetric and gravimetric uptake in highly porous materials for clean energy Chen, Zhijie; Li, Penghao; Anderson, Ryther Science, Vol. 368, Issue 6488 https://doi.org/10.1126/science.aaz8881	journal	April 2020
A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area Ferey, G.; Mellot-Draznieks, C.; Serre, C. Science, Vol. 309, Issue 5743, p. 2040-2042 https://doi.org/10.1126/science.1116275	journal	September 2005
Adding to the Arsenal of Zirconium-Based Metal-Organic Frameworks: the Topology as a Platform for Solvent-Assisted Metal Incorporation : Adding to the Arsenal of Zirconium-Based Metal-Organic Frameworks: the Topology as a Platform for Solvent-Assisted Metal Incorporation Liu, Tian-Fu; Vermeulen, Nicolaas A.; Howarth, Ashlee J. European Journal of Inorganic Chemistry, Vol. 2016, Issue 27 https://doi.org/10.1002/ejic.201600627	journal	July 2016
Water Adsorption in Porous Metal–Organic Frameworks and Related Materials Furukawa, Hiroyasu; Gándara, Felipe; Zhang, Yue-Biao Journal of the American Chemical Society, Vol. 136, Issue 11, p. 4369-4381 https://doi.org/10.1021/ja500330a	journal	March 2014
Usefulness of CO2 adsorption at 273 K for the characterization of porous carbons Lozano-Castelló, D.; Cazorla-Amorós, D.; Linares-Solano, A. Carbon, Vol. 42, Issue 7 https://doi.org/10.1016/j.carbon.2004.01.037	journal	January 2004
Rotational Dynamics of Linkers in Metal–Organic Frameworks Gonzalez-Nelson, Adrian; Coudert, François-Xavier; van der Veen, Monique Nanomaterials, Vol. 9, Issue 3 https://doi.org/10.3390/nano9030330	journal	March 2019
A Chemically Functionalizable Nanoporous Material [Cu₃(TMA)₂(H₂O)₃]_n Chui, Stephen S.-Y.; Lo, Samuel M.-F.; Charmant, Jonathan P. H. Science, Vol. 283, Issue 5405, p. 1148-1150 https://doi.org/10.1126/science.283.5405.1148	journal	February 1999
Mesoporous Metal-Organic Frameworks: Synthetic Strategies and Emerging Applications Liu, Dingxin; Zou, Dianting; Zhu, Haolin Small, Vol. 14, Issue 37 https://doi.org/10.1002/smll.201801454	journal	August 2018
Surface Area, Pore Volume Distribution, and Acidity in Mesoporous Expanded Clay Catalysts from Hybrid Density Functional Theory (DFT) and Adsorption Microcalorimetry Methods Occelli, M. L.; Olivier, J. P.; Perdigon-Melon, J. A. Langmuir, Vol. 18, Issue 25 https://doi.org/10.1021/la020567o	journal	November 2002
A facile solvent-free synthesis route for the assembly of a highly CO ₂ selective and H ₂ S tolerant NiSIFSIX metal–organic framework Shekhah, Osama; Belmabkhout, Youssef; Adil, Karim Chemical Communications, Vol. 51, Issue 71 https://doi.org/10.1039/C5CC04487A	journal	January 2015
Revisiting the structural homogeneity of NU-1000, a Zr-based metal–organic framework Islamoglu, Timur; Otake, Ken-ichi; Li, Peng CrystEngComm, Vol. 20, Issue 39 https://doi.org/10.1039/C8CE00455B	journal	January 2018
Large-Pore Apertures in a Series of Metal-Organic Frameworks Deng, H.; Grunder, S.; Cordova, K. E. Science, Vol. 336, Issue 6084, p. 1018-1023 https://doi.org/10.1126/science.1220131	journal	May 2012
Highly efficient separation of carbon dioxide by a metal-organic framework replete with open metal sites Britt, D.; Furukawa, H.; Wang, B. Proceedings of the National Academy of Sciences, Vol. 106, Issue 49, p. 20637-20640 https://doi.org/10.1073/pnas.0909718106	journal	November 2009
Function-led design of new porous materials Slater, A. G.; Cooper, A. I. Science, Vol. 348, Issue 6238 https://doi.org/10.1126/science.aaa8075	journal	May 2015
Accurate Characterization of the Pore Volume in Microporous Crystalline Materials Ongari, Daniele; Boyd, Peter G.; Barthel, Senja Langmuir, Vol. 33, Issue 51 https://doi.org/10.1021/acs.langmuir.7b01682	journal	July 2017
Adsorption methods for the characterization of porous materials Sing, Kenneth S. W. Advances in Colloid and Interface Science, Vol. 76-77 https://doi.org/10.1016/S0001-8686(98)00038-4	journal	July 1998
Progress in the Physisorption Characterization of Nanoporous Gas Storage Materials Cychosz, Katie A.; Thommes, Matthias Engineering, Vol. 4, Issue 4 https://doi.org/10.1016/j.eng.2018.06.001	journal	August 2018
A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability Cavka, Jasmina Hafizovic; Jakobsen, Søren; Olsbye, Unni Journal of the American Chemical Society, Vol. 130, Issue 42, p. 13850-13851 https://doi.org/10.1021/ja8057953	journal	October 2008
Deciphering the Relations between Pore Structure and Adsorption Behavior in Metal–Organic Frameworks: Unexpected Lessons from Argon Adsorption on Copper–Benzene-1,3,5-tricarboxylate Dantas, Silvio; Sarkisov, Lev; Neimark, Alexander V. Journal of the American Chemical Society, Vol. 141, Issue 21 https://doi.org/10.1021/jacs.9b00906	journal	May 2019
Using molecular simulation to characterise metal–organic frameworks for adsorption applications Düren, Tina; Bae, Youn-Sang; Snurr, Randall Q. Chemical Society Reviews, Vol. 38, Issue 5, p. 1237-1247 https://doi.org/10.1039/b803498m	journal	January 2009
Metal-Organic Frameworks with a Three-Dimensional Ordered Macroporous Structure: Dynamic Photonic Materials Wu, Yi-nan; Li, Fengting; Zhu, Wei Angewandte Chemie International Edition, Vol. 50, Issue 52 https://doi.org/10.1002/anie.201104597	journal	October 2011
Ordered porous materials for emerging applications Davis, Mark E. Nature, Vol. 417, Issue 6891, p. 813-821 https://doi.org/10.1038/nature00785	journal	June 2002
Actinide-based MOFs: a middle ground in solution and solid-state structural motifs Dolgopolova, Ekaterina A.; Rice, Allison M.; Shustova, Natalia B. Chemical Communications, Vol. 54, Issue 50 https://doi.org/10.1039/C7CC09780H	journal	January 2018
Consistency of carbon nanopore characteristics derived from adsorption of simple gases and 2D-NLDFT models. Advantages of using adsorption isotherms of oxygen (O2) at 77 K Jagiello, Jacek; Kenvin, Jeffrey Journal of Colloid and Interface Science, Vol. 542 https://doi.org/10.1016/j.jcis.2019.01.116	journal	April 2019
The state of the field: from inception to commercialization of metal–organic frameworks Chen, Zhijie; Wasson, Megan C.; Drout, Riki J. Faraday Discussions, Vol. 225 https://doi.org/10.1039/D0FD00103A	journal	January 2021
Mesoporous metal–organic framework materials Xuan, Weimin; Zhu, Chengfeng; Liu, Yan Chem. Soc. Rev., Vol. 41, Issue 5 https://doi.org/10.1039/C1CS15196G	journal	January 2012
Rapid Quantification of Mass Transfer Barriers in Metal–Organic Framework Crystals Son, Florencia A.; Bukowski, Brandon C.; Islamoglu, Timur Chemistry of Materials https://doi.org/10.1021/acs.chemmater.1c02462	journal	November 2021
Reticular Access to Highly Porous acs -MOFs with Rigid Trigonal Prismatic Linkers for Water Sorption Chen, Zhijie; Li, Penghao; Zhang, Xuan Journal of the American Chemical Society, Vol. 141, Issue 7 https://doi.org/10.1021/jacs.8b13710	journal	February 2019
Recommendations for the characterization of porous solids (Technical Report) Rouquerol, J.; Avnir, D.; Fairbridge, C. W. Pure and Applied Chemistry, Vol. 66, Issue 8, p. 1739-1758 https://doi.org/10.1351/pac199466081739	journal	January 1994
Design and its limitations in the construction of bi- and poly-nuclear coordination complexes and coordination polymers (aka MOFs): a personal view Robson, R. Dalton Transactions, Issue 38 https://doi.org/10.1039/B805617J	journal	January 2008
Assessing surface chemistry and pore structure of active carbons by a combination of physisorption (H2O, Ar, N2, CO2), XPS and TPD-MS Thommes, M.; Morlay, C.; Ahmad, R. Adsorption, Vol. 17, Issue 3 https://doi.org/10.1007/s10450-011-9360-4	journal	April 2011
Application of Consistency Criteria To Calculate BET Areas of Micro- And Mesoporous Metal–Organic Frameworks Gómez-Gualdrón, Diego A.; Moghadam, Peyman Z.; Hupp, Joseph T. Journal of the American Chemical Society, Vol. 138, Issue 1 https://doi.org/10.1021/jacs.5b10266	journal	December 2015
Applications of hierarchically structured porous materials from energy storage and conversion, catalysis, photocatalysis, adsorption, separation, and sensing to biomedicine Sun, Ming-Hui; Huang, Shao-Zhuan; Chen, Li-Hua Chemical Society Reviews, Vol. 45, Issue 12 https://doi.org/10.1039/C6CS00135A	journal	January 2016
Vapor-Phase Metalation by Atomic Layer Deposition in a Metal–Organic Framework Mondloch, Joseph E.; Bury, Wojciech; Fairen-Jimenez, David Journal of the American Chemical Society, Vol. 135, Issue 28, p. 10294-10297 https://doi.org/10.1021/ja4050828	journal	May 2013
Density functional theory methods for characterization of porous materials Landers, John; Gor, Gennady Yu.; Neimark, Alexander V. Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 437 https://doi.org/10.1016/j.colsurfa.2013.01.007	journal	November 2013
Calculating Geometric Surface Areas as a Characterization Tool for Metal−Organic Frameworks Düren, Tina; Millange, Franck; Férey, Gérard The Journal of Physical Chemistry C, Vol. 111, Issue 42 https://doi.org/10.1021/jp074723h	journal	October 2007
Adsorption of Gases in Multimolecular Layers Brunauer, Stephen; Emmett, P. H.; Teller, Edward Journal of the American Chemical Society, Vol. 60, Issue 2, p. 309-319 https://doi.org/10.1021/ja01269a023	journal	February 1938
The Use of Low Temperature van der Waals Adsorption Isotherms in Determining the Surface Area of Iron Synthetic Ammonia Catalysts Emmett, P. H.; Brunauer, S. Journal of the American Chemical Society, Vol. 59, Issue 8 https://doi.org/10.1021/ja01287a041	journal	August 1937
Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report) Thommes, Matthias; Kaneko, Katsumi; Neimark, Alexander V. Pure and Applied Chemistry, Vol. 87, Issue 9-10 https://doi.org/10.1515/pac-2014-1117	journal	October 2015
Surface Area Determination of Porous Materials Using the Brunauer–Emmett–Teller (BET) Method: Limitations and Improvements Sinha, Priya; Datar, Archit; Jeong, Chungsik The Journal of Physical Chemistry C, Vol. 123, Issue 33 https://doi.org/10.1021/acs.jpcc.9b02116	journal	July 2019
Ultrahigh porosity in mesoporous MOFs: promises and limitations Senkovska, Irena; Kaskel, Stefan Chemical Communications, Vol. 50, Issue 54 https://doi.org/10.1039/c4cc00524d	journal	January 2014
The Chemistry and Applications of Metal-Organic Frameworks Furukawa, H.; Cordova, K. E.; O'Keeffe, M. Science, Vol. 341, Issue 6149, p. 1230444-1230444 https://doi.org/10.1126/science.1230444	journal	August 2013
Activation of metal–organic framework materials Mondloch, Joseph E.; Karagiaridi, Olga; Farha, Omar K. CrystEngComm, Vol. 15, Issue 45 https://doi.org/10.1039/c3ce41232f	journal	January 2013
Insights on Adsorption Characterization of Metal-Organic Frameworks: A Benchmark Study on the Novel soc-MOF Moellmer, J.; Celer, E. B.; Luebke, R. Microporous and Mesoporous Materials, Vol. 129, Issue 3 https://doi.org/10.1016/j.micromeso.2009.06.014	journal	April 2010
Hierarchically Engineered Mesoporous Metal-Organic Frameworks toward Cell-free Immobilized Enzyme Systems Li, Peng; Chen, Qishui; Wang, Timothy C. Chem, Vol. 4, Issue 5 https://doi.org/10.1016/j.chempr.2018.03.001	journal	May 2018
Flexible metal–organic frameworks Schneemann, A.; Bon, V.; Schwedler, I. Chem. Soc. Rev., Vol. 43, Issue 16 https://doi.org/10.1039/C4CS00101J	journal	January 2014
Applicability of the BET Method for Determining Surface Areas of Microporous Metal−Organic Frameworks Walton, Krista S.; Snurr, Randall Q. Journal of the American Chemical Society, Vol. 129, Issue 27 https://doi.org/10.1021/ja071174k	journal	July 2007
Physisorption Hysteresis Loops and the Characterization of Nanoporous Materials Sing, Kenneth S. W.; Williams, Ruth T. Adsorption Science & Technology, Vol. 22, Issue 10 https://doi.org/10.1260/0263617053499032	journal	December 2004
Exceptional chemical and thermal stability of zeolitic imidazolate frameworks Park, K. S.; Ni, Z.; Cote, A. P. Proceedings of the National Academy of Sciences, Vol. 103, Issue 27, p. 10186-10191 https://doi.org/10.1073/pnas.0602439103	journal	June 2006
Fiber Composites of Metal–Organic Frameworks Ma, Kaikai; Idrees, Karam B.; Son, Florencia A. Chemistry of Materials, Vol. 32, Issue 17 https://doi.org/10.1021/acs.chemmater.0c02379	journal	August 2020
The Adsorption of Gases on Plane Surfaces of Glass, mica and Platinum. Langmuir, Irving Journal of the American Chemical Society, Vol. 40, Issue 9 https://doi.org/10.1021/ja02242a004	journal	September 1918
The use of gas adsorption for the characterization of porous solids Sing, Kenneth S. W. Colloids and Surfaces, Vol. 38, Issue 1 https://doi.org/10.1016/0166-6622(89)80148-9	journal	January 1989
Advancement of Actinide Metal–Organic Framework Chemistry via Synthesis of Pu-UiO-66 Hastings, Ashley M.; Ray, Debmalya; Jeong, WooSeok Journal of the American Chemical Society, Vol. 142, Issue 20 https://doi.org/10.1021/jacs.0c01895	journal	April 2020
A historical overview of the activation and porosity of metal–organic frameworks Zhang, Xuan; Chen, Zhijie; Liu, Xinyao Chemical Society Reviews, Vol. 49, Issue 20 https://doi.org/10.1039/D0CS00997K	journal	January 2020
Tailoring porosity and rotational dynamics in a series of octacarboxylate metal-organic frameworks Moreau, Florian; Kolokolov, Daniil I.; Stepanov, Alexander G. Proceedings of the National Academy of Sciences, Vol. 114, Issue 12 https://doi.org/10.1073/pnas.1615172114	journal	March 2017
Opening the Gate: Framework Flexibility in ZIF-8 Explored by Experiments and Simulations Fairen-Jimenez, D.; Moggach, S. A.; Wharmby, M. T. Journal of the American Chemical Society, Vol. 133, Issue 23 https://doi.org/10.1021/ja202154j	journal	June 2011
Testing the feasibility of using the density functional theory route for pore size distribution calculations of ordered microporous carbons Roussel, T.; Jagiello, J.; Pellenq, R. J. -M. Molecular Simulation, Vol. 32, Issue 7 https://doi.org/10.1080/08927020500517231	journal	June 2006
Development of a Cambridge Structural Database Subset: A Collection of Metal–Organic Frameworks for Past, Present, and Future Moghadam, Peyman Z.; Li, Aurelia; Wiggin, Seth B. Chemistry of Materials, Vol. 29, Issue 7 https://doi.org/10.1021/acs.chemmater.7b00441	journal	March 2017
Characterization of porous materials using combined small-angle X-ray and neutron scattering techniques Hu, Naiping; Borkar, Neha; Kohls, Doug Journal of Membrane Science, Vol. 379, Issue 1-2 https://doi.org/10.1016/j.memsci.2011.05.053	journal	September 2011
Design and synthesis of an exceptionally stable and highly porous metal-organic framework Li, Hailian; Eddaoudi, Mohamed; M., O'Keeffe Nature, Vol. 402, Issue 6759, p. 276-279 https://doi.org/10.1038/46248	journal	November 1999
Langmuir’s Theory of Adsorption: A Centennial Review Swenson, Hans; Stadie, Nicholas P. Langmuir, Vol. 35, Issue 16 https://doi.org/10.1021/acs.langmuir.9b00154	journal	March 2019
Porous Solids by Design:[Zn(4,4′-bpy)2(SiF6)]n·xDMF, a Single Framework Octahedral Coordination Polymer with Large Square Channels Subramanian, S.; Zaworotko, Michael J. Angewandte Chemie International Edition in English, Vol. 34, Issue 19 https://doi.org/10.1002/anie.199521271	journal	October 1995
NanoMOFs: little crystallites for substantial applications Majewski, M. B.; Noh, H.; Islamoglu, T. Journal of Materials Chemistry A, Vol. 6, Issue 17 https://doi.org/10.1039/C8TA02132E	journal	January 2018
Metal–Organic Framework Thin Films: From Fundamentals to Applications. Bétard, Angélique; Fischer, Roland A. Chemical Reviews, Vol. 112, Issue 2, p. 1055-1083 https://doi.org/10.1021/cr200167v	journal	September 2011
Mercury Porosimetry: A General (Practical) Overview Giesche, Herbert Particle & Particle Systems Characterization, Vol. 23, Issue 1 https://doi.org/10.1002/ppsc.200601009	journal	June 2006
Description of Gas Adsorption Isotherms on Porous and Dispersed Systems with the Excess Surface Work Model Adolphs, Jürgen; Setzer, Max Josef Journal of Colloid and Interface Science, Vol. 207, Issue 2 https://doi.org/10.1006/jcis.1998.5786	journal	November 1998
The use of van der Waals Adsorption Isotherms in Determining the Surface area of iron Synthetic Ammonia Catalysts Brunauer, Stephen; Emmett, P. H. Journal of the American Chemical Society, Vol. 57, Issue 9 https://doi.org/10.1021/ja01312a503	journal	September 1935

Similar Records

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

Technical Report · 2015 · OSTI ID:1209545

Zhou, Hongcai J

Preparation and characterization of ordered porous carbons for increasing hydrogen storage behaviors

Journal Article · 2011 · Journal of Solid State Chemistry · OSTI ID:21580018

Lee, Seul-Yi; Park, Soo-Jin

New Carbon-Based Porous Materials with Increased Heats of Adsorption for Hydrogen Storage

Technical Report · 2014 · OSTI ID:1163140

Snurr, Randall Q.; Hupp, Joseph T.; Kanatzidis, Mercouri G.; +1 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
metal–organic frameworks
gas adsorption
surface area
pore size distribution
pore volume
porosity

Title: Are you using the right probe molecules for assessing the textural properties of metal–organic frameworks?

Citation Formats

References (72)

Similar Records

Related Subjects