Statistical mechanical model of gas adsorption in porous crystals with dynamic moieties

Simon, Cory M.; Braun, Efrem; Carraro, Carlo; Smit, Berend

doi:10.1073/pnas.1613874114

Title: Statistical mechanical model of gas adsorption in porous crystals with dynamic moieties

Journal Article · 03 January 2017 · Proceedings of the National Academy of Sciences of the United States of America

DOI: https://doi.org/10.1073/pnas.1613874114 · OSTI ID:1388053

^[1]; Braun, Efrem ^[1]; Carraro, Carlo ^[1]; Smit, Berend ^[2]

Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Valais Ecole Polytechnique Federale de Lausanne (EPFL), Sion (Switzerland)

Some nanoporous, crystalline materials possess dynamic constituents, for example, rotatable moieties. These moieties can undergo a conformation change in response to the adsorption of guest molecules, which qualitatively impacts adsorption behavior. Here, we pose and solve a statistical mechanical model of gas adsorption in a porous crystal whose cages share a common ligand that can adopt two distinct rotational conformations. Guest molecules incentivize the ligands to adopt a different rotational configuration than maintained in the empty host. Our model captures inflections, steps, and hysteresis that can arise in the adsorption isotherm as a signature of the rotating ligands. The insights disclosed by our simple model contribute a more intimate understanding of the response and consequence of rotating ligands integrated into porous materials to harness them for gas storage and separations, chemical sensing, drug delivery, catalysis, and nanoscale devices. Particularly, our model reveals design strategies to exploit these moving constituents and engineer improved adsorbents with intrinsic thermal management for pressure-swing adsorption processes.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001015

OSTI ID:: 1388053

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Vol. 114, Issue 3; Related Information: CGS partners with University of California, Berkeley; University of California, Davis; Lawrence Berkeley National Laboratory; University of Minnesota; National Energy Technology Laboratory; Texas A&M University; ISSN 0027-8424

Publisher:: National Academy of Sciences, Washington, DC (United States)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 36 works

Citation information provided by
Web of Science

References (67)

Flexibility in metal-organic framework materials: Impact on sorption properties Fletcher, Ashleigh J.; Thomas, K. Mark; Rosseinsky, Matthew J. Journal of Solid State Chemistry, Vol. 178, Issue 8 https://doi.org/10.1016/j.jssc.2005.05.019	journal	August 2005
A Pillared-Layer Coordination Polymer with a Rotatable Pillar Acting as a Molecular Gate for Guest Molecules Seo, Joobeom; Matsuda, Ryotaro; Sakamoto, Hirotoshi Journal of the American Chemical Society, Vol. 131, Issue 35 https://doi.org/10.1021/ja904363b	journal	September 2009
Quantifying Large Effects of Framework Flexibility on Diffusion in MOFs: CH ₄ and CO ₂ in ZIF-8 Haldoupis, Emmanuel; Watanabe, Taku; Nair, Sankar ChemPhysChem, Vol. 13, Issue 15 https://doi.org/10.1002/cphc.201200529	journal	July 2012
Hydrogen bond-regulated microporous nature of copper complex-assembled microcrystals Li, Di; Kaneko, Katsumi Chemical Physics Letters, Vol. 335, Issue 1-2 https://doi.org/10.1016/S0009-2614(00)01419-6	journal	February 2001
Free energy landscapes for the thermodynamic understanding of adsorption-induced deformations and structural transitions in porous materials Bousquet, D.; Coudert, F. -X.; Boutin, A. The Journal of Chemical Physics, Vol. 137, Issue 4 https://doi.org/10.1063/1.4738776	journal	July 2012
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
Metastable Sorption State of a Metal–Organic Porous Material Determined by In Situ Synchrotron Powder Diffraction Kubota, Yoshiki; Takata, Masaki; Matsuda, Ryotaro Angewandte Chemie, Vol. 118, Issue 30 https://doi.org/10.1002/ange.200600976	journal	July 2006
Metal–organic framework materials as catalysts Lee, JeongYong; Farha, Omar K.; Roberts, John Chemical Society Reviews, Vol. 38, Issue 5, p. 1450-1459 https://doi.org/10.1039/b807080f	journal	January 2009
Optimum Conditions for Adsorptive Storage Bhatia, Suresh K.; Myers, Alan L. Langmuir, Vol. 22, Issue 4 https://doi.org/10.1021/la0523816	journal	February 2006
Isosteric Heat of Adsorption: Theory and Experiment Sircar, S.; Mohr, R.; Ristic, C. The Journal of Physical Chemistry B, Vol. 103, Issue 31 https://doi.org/10.1021/jp9903817	journal	August 1999
Flexible Porous Metal-Organic Frameworks for a Controlled Drug Delivery Horcajada, Patricia; Serre, Christian; Maurin, Guillaume Journal of the American Chemical Society, Vol. 130, Issue 21 https://doi.org/10.1021/ja710973k	journal	May 2008
Rotating Phenyl Rings as a Guest-Dependent Switch in Two-Dimensional Metal–Organic Frameworks Murdock, Christopher R.; McNutt, Nicholas W.; Keffer, David J. Journal of the American Chemical Society, Vol. 136, Issue 2 https://doi.org/10.1021/ja4088709	journal	January 2014
The role of dynamic conformational ensembles in biomolecular recognition Boehr, David D.; Nussinov, Ruth; Wright, Peter E. Nature Chemical Biology, Vol. 5, Issue 11 https://doi.org/10.1038/nchembio.232	journal	October 2009
Isosteric heats of multicomponent adsorption: thermodynamics and computer simulations Karavias, Fokion.; Myers, Alan L. Langmuir, Vol. 7, Issue 12 https://doi.org/10.1021/la00060a035	journal	December 1991
Role of Solvent-Host Interactions That Lead to Very Large Swelling of Hybrid Frameworks Serre, C.; Mellot-Draznieks, C.; Surble, S. Science, Vol. 315, Issue 5820 https://doi.org/10.1126/science.1137975	journal	March 2007
Exact matrix treatment of an osmotic ensemble model of adsorption and pressure induced structural transitions in metal organic frameworks Dunne, Lawrence J.; Manos, George Dalton Transactions, Vol. 45, Issue 10 https://doi.org/10.1039/C5DT03248B	journal	January 2016
Reticular synthesis and the design of new materials Yaghi, Omar M.; O'Keeffe, Michael; Ockwig, Nathan W. Nature, Vol. 423, Issue 6941, p. 705-714 https://doi.org/10.1038/nature01650	journal	June 2003
The Key–Lock Theory and the Induced Fit Theory Koshland, Daniel E. Angewandte Chemie International Edition in English, Vol. 33, Issue 2324 https://doi.org/10.1002/anie.199423751	journal	January 1995
Structural Origin of Unusual CO ₂ Adsorption Behavior of a Small-Pore Aluminum Bisphosphonate MOF Llewellyn, Philip L.; Garcia-Rates, Miquel; Gaberová, Lucia The Journal of Physical Chemistry C, Vol. 119, Issue 8 https://doi.org/10.1021/jp512596u	journal	February 2015
Spin crossover phenomena in Fe(ii) complexes Gütlich, Philipp; Garcia, Yann; Goodwin, Harold A. Chemical Society Reviews, Vol. 29, Issue 6 https://doi.org/10.1039/b003504l	journal	January 2000
Commensurate phases, incommensurate phases and the devil's staircase Bak, P. Reports on Progress in Physics, Vol. 45, Issue 6 https://doi.org/10.1088/0034-4885/45/6/001	journal	June 1982
Introduction to Metal–Organic Frameworks Zhou, Hong-Cai; Long, Jeffrey R.; Yaghi, Omar M. Chemical Reviews, Vol. 112, Issue 2, p. 673-674 https://doi.org/10.1021/cr300014x	journal	September 2011
Dynamic Motion of Building Blocks in Porous Coordination Polymers Horike, Satoshi; Matsuda, Ryotaro; Tanaka, Daisuke Angewandte Chemie International Edition, Vol. 45, Issue 43 https://doi.org/10.1002/anie.200603196	journal	November 2006
Exploration of Gate-Opening and Breathing Phenomena in a Tailored Flexible Metal–Organic Framework Hyun, Sung-min; Lee, Jae Hwa; Jung, Gwan Yeong Inorganic Chemistry, Vol. 55, Issue 4 https://doi.org/10.1021/acs.inorgchem.5b02874	journal	January 2016
The role of metal–organic frameworks in a carbon-neutral energy cycle Schoedel, Alexander; Ji, Zhe; Yaghi, Omar M. Nature Energy, Vol. 1, Issue 4 https://doi.org/10.1038/nenergy.2016.34	journal	April 2016
Selective gas adsorption and separation in metal–organic frameworks Li, Jian-Rong; Kuppler, Ryan J.; Zhou, Hong-Cai Chemical Society Reviews, Vol. 38, Issue 5, p. 1477-1504 https://doi.org/10.1039/b802426j	journal	January 2009
Understanding DABCO Nanorotor Dynamics in Isostructural Metal–Organic Frameworks Burtch, Nicholas C.; Torres-Knoop, Ariana; Foo, Guo Shiou The Journal of Physical Chemistry Letters, Vol. 6, Issue 5 https://doi.org/10.1021/jz502653y	journal	February 2015
Dipolar molecular rotors in the metal–organic framework crystal IRMOF-2 Winston, Erick B.; Lowell, Peter J.; Vacek, Jaroslav Physical Chemistry Chemical Physics, Vol. 10, Issue 34 https://doi.org/10.1039/b808104b	journal	January 2008
Thermodynamics of Guest-Induced Structural Transitions in Hybrid Organic−Inorganic Frameworks Coudert, François-Xavier; Jeffroy, Marie; Fuchs, Alain H. Journal of the American Chemical Society, Vol. 130, Issue 43 https://doi.org/10.1021/ja805129c	journal	October 2008
Rigid and Flexible: A Highly Porous Metal–Organic Framework with Unusual Guest-Dependent Dynamic Behavior Dybtsev, Danil N.; Chun, Hyungphil; Kim, Kimoon Angewandte Chemie, Vol. 116, Issue 38 https://doi.org/10.1002/ange.200460712	journal	September 2004
A molecular shuttle that operates inside a metal–organic framework Zhu, Kelong; O'Keefe, Christopher A.; Vukotic, V. Nicholas Nature Chemistry, Vol. 7, Issue 6 https://doi.org/10.1038/nchem.2258	journal	May 2015
Artificial Molecular Rotors Kottas, Gregg S.; Clarke, Laura I.; Horinek, Dominik Chemical Reviews, Vol. 105, Issue 4 https://doi.org/10.1021/cr0300993	journal	April 2005
On the Thermodynamics of Framework Breathing: A Free Energy Model for Gas Adsorption in MIL-53 Ghysels, An; Vanduyfhuys, Louis; Vandichel, Matthias The Journal of Physical Chemistry C, Vol. 117, Issue 22 https://doi.org/10.1021/jp311601q	journal	May 2013
Selective adsorption of ethylene over ethane and propylene over propane in the metal–organic frameworks M2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Zn) Geier, Stephen J.; Mason, Jarad A.; Bloch, Eric D. Chemical Science, Vol. 4, Issue 5 https://doi.org/10.1039/c3sc00032j	journal	January 2013
Dynamics of Benzene Rings in MIL-53(Cr) and MIL-47(V) Frameworks Studied by 2H NMR Spectroscopy Kolokolov, Daniil I.; Jobic, Hervé; Stepanov, Alexander G. Angewandte Chemie International Edition, Vol. 49, Issue 28 https://doi.org/10.1002/anie.201001238	journal	May 2010
Control of Molecular Rotor Rotational Frequencies in Porous Coordination Polymers Using a Solid-Solution Approach Inukai, Munehiro; Fukushima, Tomohiro; Hijikata, Yuh Journal of the American Chemical Society, Vol. 137, Issue 38 https://doi.org/10.1021/jacs.5b05413	journal	September 2015
Optimizing nanoporous materials for gas storage Simon, Cory M.; Kim, Jihan; Lin, Li-Chiang Physical Chemistry Chemical Physics, Vol. 16, Issue 12 https://doi.org/10.1039/c3cp55039g	journal	January 2014
Synthesis, Structure and Properties of Related Microporous N , N ‘-Piperazinebismethylenephosphonates of Aluminum and Titanium Serre, Christian; Groves, John A.; Lightfoot, Philip Chemistry of Materials, Vol. 18, Issue 6 https://doi.org/10.1021/cm052149l	journal	March 2006
Responsive Metal–Organic Frameworks and Framework Materials: Under Pressure, Taking the Heat, in the Spotlight, with Friends Coudert, François-Xavier Chemistry of Materials, Vol. 27, Issue 6 https://doi.org/10.1021/acs.chemmater.5b00046	journal	February 2015
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
Selective CO2 uptake and inverse CO2/C2H2 selectivity in a dynamic bifunctional metal–organic framework Yang, Wenbin; Davies, Andrew J.; Lin, Xiang Chemical Science, Vol. 3, Issue 10 https://doi.org/10.1039/c2sc20443f	journal	January 2012
A pressure-amplifying framework material with negative gas adsorption transitions Krause, Simon; Bon, Volodymyr; Senkovska, Irena Nature, Vol. 532, Issue 7599 https://doi.org/10.1038/nature17430	journal	April 2016
Adsorption induced transitions in soft porous crystals: An osmotic potential approach to multistability and intermediate structures Bousquet, David; Coudert, François-Xavier; Fossati, Alexandre G. J. The Journal of Chemical Physics, Vol. 138, Issue 17 https://doi.org/10.1063/1.4802888	journal	May 2013
Mechanism of Breathing Transitions in Metal–Organic Frameworks Triguero, Carles; Coudert, François-Xavier; Boutin, Anne The Journal of Physical Chemistry Letters, Vol. 2, Issue 16 https://doi.org/10.1021/jz2008769	journal	July 2011
Two-Step Adsorption/Desorption on a Jungle-Gym-Type Porous Coordination Polymer Uemura, Kazuhiro; Yamasaki, Yukari; Komagawa, Yuki Angewandte Chemie, Vol. 119, Issue 35 https://doi.org/10.1002/ange.200702390	journal	September 2007
A Switchable Molecular Rotator: Neutron Spectroscopy Study on a Polymeric Spin-Crossover Compound Rodríguez-Velamazán, J. Alberto; González, Miguel A.; Real, José A. Journal of the American Chemical Society, Vol. 134, Issue 11 https://doi.org/10.1021/ja206228n	journal	March 2012
Structure and Dynamics of the Functionalized MOF Type UiO-66(Zr): NMR and Dielectric Relaxation Spectroscopies Coupled with DFT Calculations Devautour-Vinot, Sabine; Maurin, Guillaume; Serre, Christian Chemistry of Materials, Vol. 24, Issue 11 https://doi.org/10.1021/cm300863c	journal	May 2012
Gas Storage in Nanoporous Materials Morris, Russell E.; Wheatley, Paul S. Angewandte Chemie International Edition, Vol. 47, Issue 27 https://doi.org/10.1002/anie.200703934	journal	June 2008
Artificial Molecular Machines Balzani, Vincenzo; Credi, Alberto; Raymo, Françisco M. Angewandte Chemie, Vol. 39, Issue 19 https://doi.org/10.1002/1521-3773(20001002)39:19<3348::AID-ANIE3348>3.0.CO;2-X	journal	October 2000
Noble Gas Adsorption in Copper Trimesate, HKUST-1: An Experimental and Computational Study Hulvey, Zeric; Lawler, Keith V.; Qiao, Zhiwei The Journal of Physical Chemistry C, Vol. 117, Issue 39 https://doi.org/10.1021/jp408034u	journal	September 2013
Framework mobility in the metal–organic framework crystal IRMOF-3: Evidence for aromatic ring and amine rotation Morris, William; Taylor, R. E.; Dybowski, C. Journal of Molecular Structure, Vol. 1004, Issue 1-3, p. 94-101 https://doi.org/10.1016/j.molstruc.2011.07.037	journal	October 2011
Behavior and performance of adsorptive natural gas storage cylinders during discharge Chang, K. J.; Talu, Orhan Applied Thermal Engineering, Vol. 16, Issue 5 https://doi.org/10.1016/1359-4311(95)00017-8	journal	May 1996
Understanding Inflections and Steps in Carbon Dioxide Adsorption Isotherms in Metal-Organic Frameworks Walton, Krista S.; Millward, Andrew R.; Dubbeldam, David Journal of the American Chemical Society, Vol. 130, Issue 2, p. 406-407 https://doi.org/10.1021/ja076595g	journal	January 2008
Direct Structural Identification of Gas Induced Gate-Opening Coupled with Commensurate Adsorption in a Microporous Metal-Organic Framework Banerjee, Debasis; Wang, Hao; Plonka, Anna M. Chemistry - A European Journal, Vol. 22, Issue 33 https://doi.org/10.1002/chem.201601784	journal	July 2016
Ethane/Ethene Separation Turned on Its Head: Selective Ethane Adsorption on the Metal−Organic Framework ZIF-7 through a Gate-Opening Mechanism Gücüyener, Canan; van den Bergh, Johan; Gascon, Jorge Journal of the American Chemical Society, Vol. 132, Issue 50 https://doi.org/10.1021/ja1089765	journal	December 2010
Adsorption isotherm model for multicomponent adsorbate—adsorbate interactions Moreau, Michel; Valentin, Patrick; Vidal-Madjar, Claire Journal of Colloid and Interface Science, Vol. 141, Issue 1 https://doi.org/10.1016/0021-9797(91)90308-U	journal	January 1991
Metal–organic frameworks based on flexible ligands (FL-MOFs): structures and applications Lin, Zu-Jin; Lü, Jian; Hong, Maochun Chem. Soc. Rev., Vol. 43, Issue 16 https://doi.org/10.1039/C3CS60483G	journal	January 2014
Large breathing effects in three-dimensional porous hybrid matter: facts, analyses, rules and consequences Férey, Gérard; Serre, Christian Chemical Society Reviews, Vol. 38, Issue 5 https://doi.org/10.1039/b804302g	journal	January 2009
Metal–Organic Framework Materials as Chemical Sensors Kreno, Lauren E.; Leong, Kirsty; Farha, Omar K. Chemical Reviews, Vol. 112, Issue 2, p. 1105-1125 https://doi.org/10.1021/cr200324t	journal	September 2011
Very Large Breathing Effect in the First Nanoporous Chromium(III)-Based Solids MIL-53 or Cr^III(OH)·{O₂C−C₆H₄−CO₂}·{HO₂C−C₆H₄−CO₂H}_x·H₂O_y Serre, Christian; Millange, Franck; Thouvenot, Christelle Journal of the American Chemical Society, Vol. 124, Issue 45, p. 13519-13526 https://doi.org/10.1021/ja0276974	journal	November 2002
Bidirectional Chemo-Switching of Spin State in a Microporous Framework Ohba, Masaaki; Yoneda, Ko; Agustí, Gloria Angewandte Chemie International Edition, Vol. 48, Issue 26 https://doi.org/10.1002/anie.200806039	journal	June 2009
Methane storage in flexible metal–organic frameworks with intrinsic thermal management Mason, Jarad A.; Oktawiec, Julia; Taylor, Mercedes K. Nature, Vol. 527, Issue 7578 https://doi.org/10.1038/nature15732	journal	October 2015
Guest-induced gate-opening of a zeolite imidazolate framework Aguado, Sonia; Bergeret, Gérard; Titus, Marc Pera New J. Chem., Vol. 35, Issue 3 https://doi.org/10.1039/C0NJ00836B	journal	January 2011
Amphidynamic Character of Crystalline MOF-5: Rotational Dynamics of Terephthalate Phenylenes in a Free-Volume, Sterically Unhindered Environment Gould, Stephanie L.; Tranchemontagne, David; Yaghi, Omar M. Journal of the American Chemical Society, Vol. 130, Issue 11, p. 3246-3247 https://doi.org/10.1021/ja077122c	journal	March 2008
Porous Coordination-Polymer Crystals with Gated Channels Specific for Supercritical Gases Kitaura, Ryo; Seki, Kenji; Akiyama, George Angewandte Chemie International Edition, Vol. 42, Issue 4 https://doi.org/10.1002/anie.200390130	journal	January 2003
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
Soft porous crystals Horike, Satoshi; Shimomura, Satoru; Kitagawa, Susumu Nature Chemistry, Vol. 1, Issue 9, p. 695-704 https://doi.org/10.1038/nchem.444	journal	November 2009

Cited By (5)

Exploiting rotational motion in molecular crystals Catalano, Luca; Naumov, Panče CrystEngComm, Vol. 20, Issue 39 https://doi.org/10.1039/c8ce00420j	journal	January 2018
Statistical mechanics of binary mixture adsorption in metal–organic frameworks in the osmotic ensemble Dunne, Lawrence J.; Manos, George Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 376, Issue 2115 https://doi.org/10.1098/rsta.2017.0151	journal	February 2018
Predicting the Features of Methane Adsorption in Large Pore Metal-Organic Frameworks for Energy Storage Manos, George; Dunne, Lawrence Nanomaterials, Vol. 8, Issue 10 https://doi.org/10.3390/nano8100818	journal	October 2018
Structural Basis of CO2 Adsorption in a Flexible Metal-Organic Framework Material Allen, Andrew; Wong-Ng, Winnie; Cockayne, Eric Nanomaterials, Vol. 9, Issue 3 https://doi.org/10.3390/nano9030354	journal	March 2019
Flexible Force Field Parameterization through Fitting on the Ab Initio-Derived Elastic Tensor Heinen, Jurn; Burtch, Nicholas C.; Walton, Krista S. Journal of Chemical Theory and Computation, Vol. 13, Issue 8 https://doi.org/10.1021/acs.jctc.7b00310	journal	July 2017

Similar Records

Syntheses, crystal structures, and water adsorption behaviors of jungle-gym-type porous coordination polymers containing nitro moieties

Journal Article · 2009 · Journal of Solid State Chemistry · OSTI ID:21372357

Uemura, Kazuhiro; Onishi, Fumiaki; Yamasaki, Yukari; +1 more

Effect of ring rotation upon gas adsorption in SIFSIX-3-M (M = Fe, Ni) pillared square grid networks

Journal Article · 2017 · Chemical Science · OSTI ID:1373592

Elsaidi, Sameh K.; Mohamed, Mona H.; Simon, Cory M.; +8 more

Distinct host-guest interaction and subdued fluorescence in a coordination network of 2,3,6,7,10,11-hexakis(phenylthio)triphenylene and silver(I) triflate

Journal Article · 2006 · Journal of Solid State Chemistry · OSTI ID:20902485

Kunhao, Li; Guo, Huang; Zhengtao, Xu; +1 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
membrane
carbon capture
materials and chemistry by design
synthesis (novel materials)
synthesis (self-assembly)
synthesis (scalable processing)

Title: Statistical mechanical model of gas adsorption in porous crystals with dynamic moieties

Citation Formats

References (67)

Cited By (5)

Similar Records

Related Subjects