Temperature-regulated guest admission and release in microporous materials

Li, Gang; Shang, Jin; Gu, Qinfen; Awati, Rohan V.; Jensen, Nathan; Grant, Andrew; Zhang, Xueying; Sholl, David S.; Liu, Jefferson Z.; Webley, Paul A.; May, Eric F.

doi:10.1038/ncomms15777

Title: Temperature-regulated guest admission and release in microporous materials

Journal Article · Fri Jun 09 00:00:00 EDT 2017 · Nature Communications

DOI:https://doi.org/10.1038/ncomms15777· OSTI ID:1374884

Li, Gang ^[1]; Shang, Jin ^[2]; Gu, Qinfen ^[3]; Awati, Rohan V. ^[4]; Jensen, Nathan ^[1]; Grant, Andrew ^[1]; Zhang, Xueying ^[5]; Sholl, David S. ^[4];

^[6]; Webley, Paul A. ^[5];

^[1]

Univ. of Western Australia, Crawley, WA (Australia). Centre for Energy
City Univ. of Hong Kong (China). School of Energy and Environmental Catalysis; Univ. of Melbourne (Australia). Dept. of Chemical and Biomolecular Engineering
Australian Nuclear Science and Technology Organisation (ANSTO), Clayton, VIC (Australia). Australian Synchrotron
Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical and Biomolecular Engineering
Univ. of Melbourne (Australia). Dept. of Chemical and Biomolecular Engineering
Monash Univ., Melbourne, VIC (Australia). Dept. of Mechanical and Aerospace Engineering

While it has long been known that some highly adsorbing microporous materials suddenly become inaccessible to guest molecules below certain temperatures, previous attempts to explain this phenomenon have failed. Here we show that this anomalous sorption behaviour is a temperature-regulated guest admission process, where the pore-keeping group’s thermal fluctuations are influenced by interactions with guest molecules. A physical model is presented to explain the atomic-level chemistry and structure of these thermally regulated micropores, which is crucial to systematic engineering of new functional materials such as tunable molecular sieves, gated membranes and controlled-release nanocontainers. The model was validated experimentally with H₂, N₂, Ar and CH₄ on three classes of microporous materials: trapdoor zeolites, supramolecular host calixarenes and metal-organic frameworks. We also demonstrate how temperature can be exploited to achieve appreciable hydrogen and methane storage in such materials without sustained pressure. Our findings also open new avenues for gas sensing and isotope separation.

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Research Organization:: Georgia Institute of Technology, Atlanta, GA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME)

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

Grant/Contract Number:: SC0012577; DE140101824; DP130103708; IC150100019

OSTI ID:: 1374884

Journal Information:: Nature Communications, Vol. 8; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 58 works

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References (60)

Temperature-triggered gate opening for gas adsorption in microporous manganese formate Kim, Hyunuk; Samsonenko, Denis G.; Yoon, Minyoung Chemical Communications, Issue 39 https://doi.org/10.1039/b811087e	journal	January 2008
An extended Langmuir model for adsorption of gas mixtures on heterogeneous surfaces Kapoor, A.; Ritter, J. A.; Yang, Ralph T. Langmuir, Vol. 6, Issue 3 https://doi.org/10.1021/la00093a022	journal	March 1990
Negative thermal expansion: a review Miller, W.; Smith, C. W.; Mackenzie, D. S. Journal of Materials Science, Vol. 44, Issue 20 https://doi.org/10.1007/s10853-009-3692-4	journal	July 2009
Thermodynamics of mixed-gas adsorption Myers, A. L.; Prausnitz, J. M. AIChE Journal, Vol. 11, Issue 1, p. 121-127 https://doi.org/10.1002/aic.690110125	journal	January 1965
A Mesh-Adjustable Molecular Sieve for General Use in Gas Separation Ma, Shengqian; Sun, Daofeng; Wang, Xi-Sen Angewandte Chemie International Edition, Vol. 46, Issue 14 https://doi.org/10.1002/anie.200604353	journal	March 2007
Exceptional Framework Flexibility and Sorption Behavior of a Multifunctional Porous Cuprous Triazolate Framework Zhang, Jie-Peng; Chen, Xiao-Ming Journal of the American Chemical Society, Vol. 130, Issue 18, p. 6010-6017 https://doi.org/10.1021/ja800550a	journal	May 2008
On the inner workings of Monte Carlo codes Dubbeldam, David; Torres-Knoop, Ariana; Walton, Krista S. Molecular Simulation, Vol. 39, Issue 14-15 https://doi.org/10.1080/08927022.2013.819102	journal	December 2013
Gas separation by adsorption processes Helfferich, Friedrich G. Reactive Polymers, Ion Exchangers, Sorbents, Vol. 9, Issue 3 https://doi.org/10.1016/0167-6989(88)90256-5	journal	December 1988
First principles derived, transferable force fields for CO2 adsorption in Na-exchanged cationic zeolites Fang, Hanjun; Kamakoti, Preeti; Ravikovitch, Peter I. Physical Chemistry Chemical Physics, Vol. 15, Issue 31 https://doi.org/10.1039/c3cp52246f	journal	January 2013
Preparation and Gas Adsorption Studies of Three Mesh-Adjustable Molecular Sieves with a Common Structure Ma, Shengqian; Sun, Daofeng; Yuan, Daqiang Journal of the American Chemical Society, Vol. 131, Issue 18 https://doi.org/10.1021/ja808896f	journal	May 2009
A Study of Heat-Treatment Induced Framework Contraction in Strontium-ETS-4 by Powder Neutron Diffraction and Vibrational Spectroscopy Nair, Sankar; Tsapatsis, Michael; Toby, Brian H. Journal of the American Chemical Society, Vol. 123, Issue 51 https://doi.org/10.1021/ja011703z	journal	December 2001
Cation Gating and Relocation during the Highly Selective “Trapdoor” Adsorption of CO ₂ on Univalent Cation Forms of Zeolite Rho Lozinska, Magdalena M.; Mowat, John P. S.; Wright, Paul A. Chemistry of Materials, Vol. 26, Issue 6 https://doi.org/10.1021/cm404028f	journal	March 2014
A crystalline organic substrate absorbs methane under STP conditions Atwood, Jerry L.; Barbour, Leonard J.; Thallapally, Praveen K. Chemical Communications, Issue 1 https://doi.org/10.1039/b416752j	journal	January 2005
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Hydrogen storage in Pd nanocrystals covered with a metal–organic framework Li, Guangqin; Kobayashi, Hirokazu; Taylor, Jared M. Nature Materials, Vol. 13, Issue 8 https://doi.org/10.1038/nmat4030	journal	July 2014
Robust dynamics Deng, Hexiang; Olson, Mark A.; Stoddart, J. Fraser Nature Chemistry, Vol. 2, Issue 6, p. 439-443 https://doi.org/10.1038/nchem.654	journal	May 2010
Data from: Temperature-regulated guest admission and release in microporous materials Li, Gang Kevin; Shang, Jin; Gu, Qinfen Dryad Digital Repository-Supplementary information for journal article at DOI: 10.1038/ncomms15777, 3 CIF files https://doi.org/10.5061/dryad.2426m	dataset	June 2017
Molecular sieve sensors for selective detection at the nanogram level Bein, Thomas; Brown, Kelly; Frye, Gregory C. Journal of the American Chemical Society, Vol. 111, Issue 19 https://doi.org/10.1021/ja00201a069	journal	September 1989
Hydrogen storage in metal–organic frameworks Murray, Leslie J.; Dincă, Mircea; Long, Jeffrey R. Chemical Society Reviews, Vol. 38, Issue 5, p. 1294-1314 https://doi.org/10.1039/b802256a	journal	January 2009
Dynamic Photo-Switching in Metal-Organic Frameworks as a Route to Low-Energy Carbon Dioxide Capture and Release Lyndon, Richelle; Konstas, Kristina; Ladewig, Bradley P. Angewandte Chemie, Vol. 125, Issue 13 https://doi.org/10.1002/ange.201206359	journal	February 2013
Separation of Hexane Isomers in a Metal-Organic Framework with Triangular Channels Herm, Z. R.; Wiers, B. M.; Mason, J. A. Science, Vol. 340, Issue 6135, p. 960-964 https://doi.org/10.1126/science.1234071	journal	May 2013
Crystalline Zeolites. I. The Properties of a New Synthetic Zeolite, Type A Breck, D. W.; Eversole, W. G.; Milton, R. M. Journal of the American Chemical Society, Vol. 78, Issue 23 https://doi.org/10.1021/ja01604a001	journal	December 1956
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
Gas Separation by Adsorption Processes Kirkby, N. Gas Separation & Purification, Vol. 2, Issue 1 https://doi.org/10.1016/0950-4214(88)80042-2	journal	March 1988
Site-Specific CO₂ Adsorption and Zero Thermal Expansion in an Anisotropic Pore Network Queen, Wendy L.; Brown, Craig M.; Britt, David K. The Journal of Physical Chemistry C, Vol. 115, Issue 50, p. 24915-24919 https://doi.org/10.1021/jp208529p	journal	December 2011
Dynamic Photo-Switching in Metal-Organic Frameworks as a Route to Low-Energy Carbon Dioxide Capture and Release Lyndon, Richelle; Konstas, Kristina; Ladewig, Bradley P. Angewandte Chemie https://doi.org/10.1002/ange.201301126	journal	February 2013
Trapdoors in zeolites De Baerdemaeker, Trees; De Vos, Dirk Nature Chemistry, Vol. 5, Issue 2 https://doi.org/10.1038/nchem.1560	journal	January 2013
Dynamic Photo-Switching in Metal-Organic Frameworks as a Route to Low-Energy Carbon Dioxide Capture and Release Lyndon, Richelle; Konstas, Kristina; Ladewig, Bradley P. Angewandte Chemie International Edition, Vol. 52, Issue 13 https://doi.org/10.1002/anie.201206359	journal	February 2013
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Unconventional, Highly Selective CO ₂ Adsorption in Zeolite SSZ-13 Hudson, Matthew R.; Queen, Wendy L.; Mason, Jarad A. Journal of the American Chemical Society, Vol. 134, Issue 4 https://doi.org/10.1021/ja210580b	journal	January 2012
Synthesis Strategies for Preparing Useful Small Pore Zeolites and Zeotypes for Gas Separations and Catalysis Moliner, Manuel; Martínez, Cristina; Corma, Avelino Chemistry of Materials, Vol. 26, Issue 1 https://doi.org/10.1021/cm4015095	journal	July 2013
Gas Separation by Adsorption Processes Yang, Ralph T. Series on Chemical Engineering https://doi.org/10.1142/p037	book	June 1997
Identification of High-CO ₂ -Capacity Cationic Zeolites by Accurate Computational Screening Fang, Hanjun; Kulkarni, Ambarish; Kamakoti, Preeti Chemistry of Materials, Vol. 28, Issue 11 https://doi.org/10.1021/acs.chemmater.6b01132	journal	May 2016
Novel low energy hydrogen–deuterium isotope breakthrough separation using a trapdoor zeolite Physick, Andrew J. W.; Wales, Dominic J.; Owens, Simon H. R. Chemical Engineering Journal, Vol. 288 https://doi.org/10.1016/j.cej.2015.11.040	journal	March 2016
RASPA: molecular simulation software for adsorption and diffusion in flexible nanoporous materials Dubbeldam, David; Calero, Sofía; Ellis, Donald E. Molecular Simulation, Vol. 42, Issue 2 https://doi.org/10.1080/08927022.2015.1010082	journal	February 2015
Crystalline molecular sieves Breck, D. W. Journal of Chemical Education, Vol. 41, Issue 12 https://doi.org/10.1021/ed041p678	journal	December 1964
A Rigid Nested Metal-Organic Framework Featuring a Thermoresponsive Gating Effect Dominated by Counterions Gao, Qiang; Xu, Jian; Cao, Dapeng Angewandte Chemie, Vol. 128, Issue 48 https://doi.org/10.1002/ange.201608250	journal	October 2016
Discriminative Separation of Gases by a “Molecular Trapdoor” Mechanism in Chabazite Zeolites Shang, Jin; Li, Gang; Singh, Ranjeet Journal of the American Chemical Society, Vol. 134, Issue 46 https://doi.org/10.1021/ja309274y	journal	November 2012
Adsorption equilibria and kinetics of CH4 and N2 on commercial zeolites and carbons Xiao, Gongkui; Li, Zhikao; Saleman, Thomas L. Adsorption, Vol. 23, Issue 1 https://doi.org/10.1007/s10450-016-9840-7	journal	November 2016
A molecular turnstile in para-octanoyl calix[4]arene nanocapsules Ananchenko, Gennady S.; Udachin, Konstantin A.; Pojarova, Michaela Chem. Commun., Issue 7 https://doi.org/10.1039/B613972H	journal	January 2007
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Understanding Carbon Dioxide Adsorption on Univalent Cation Forms of the Flexible Zeolite Rho at Conditions Relevant to Carbon Capture from Flue Gases Lozinska, Magdalena M.; Mangano, Enzo; Mowat, John P. S. Journal of the American Chemical Society, Vol. 134, Issue 42 https://doi.org/10.1021/ja3070864	journal	October 2012
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
Adsorption and Separation of CO ₂ on KFI Zeolites: Effect of Cation Type and Si/Al Ratio on Equilibrium and Kinetic Properties Remy, Tom; Peter, Sunil A.; Van Tendeloo, Leen Langmuir, Vol. 29, Issue 16 https://doi.org/10.1021/la400352r	journal	April 2013
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets Chen, Ruyi; Cui, Qirui; Liao, Liyang Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23414-3	journal	May 2021
Determination of Composition Range for “Molecular Trapdoor” Effect in Chabazite Zeolite Shang, Jin; Li, Gang; Singh, Ranjeet The Journal of Physical Chemistry C, Vol. 117, Issue 24 https://doi.org/10.1021/jp4015146	journal	June 2013
Comparison of porous and nonporous materials for methane storage Thallapally, Praveen K.; Kirby, Karen A.; Atwood, Jerry L. New J. Chem., Vol. 31, Issue 5 https://doi.org/10.1039/B610321A	journal	January 2007
Porous materials with optimal adsorption thermodynamics and kinetics for CO₂ separation Nugent, Patrick; Belmabkhout, Youssef; Burd, Stephen D. Nature, Vol. 495, Issue 7439, p. 80-84 https://doi.org/10.1038/nature11893	journal	February 2013
A Rigid Nested Metal-Organic Framework Featuring a Thermoresponsive Gating Effect Dominated by Counterions Gao, Qiang; Xu, Jian; Cao, Dapeng Angewandte Chemie International Edition, Vol. 55, Issue 48 https://doi.org/10.1002/anie.201608250	journal	October 2016
A titanosilicate molecular sieve with adjustable pores for size-selective adsorption of molecules Kuznicki, Steven M.; Bell, Valerie A.; Nair, Sankar Nature, Vol. 412, Issue 6848 https://doi.org/10.1038/35089052	journal	August 2001
Binary Adsorption Equilibrium of Carbon Dioxide and Water Vapor on Activated Alumina Li, Gang; Xiao, Penny; Webley, Paul Langmuir, Vol. 25, Issue 18 https://doi.org/10.1021/la901107s	journal	September 2009
Gas Separation by Adsorption Processes Yang, RalphT. Chemical Engineering Science, Vol. 43, Issue 4 https://doi.org/10.1016/0009-2509(88)80096-4	journal	January 1988
A Mesh-Adjustable Molecular Sieve for General Use in Gas Separation Ma, Shengqian; Sun, Daofeng; Wang, Xi-Sen Angewandte Chemie, Vol. 119, Issue 14 https://doi.org/10.1002/ange.200604353	journal	March 2007
Guest Transport in a Nonporous Organic Solid via Dynamic van der Waals Cooperativity Atwood, J. L.; Barbour, L. J.; Jerga, A. Science, Vol. 298, Issue 5595 https://doi.org/10.1126/science.1077591	journal	November 2002
Comparative Molecular Simulation Study of CO ₂ /N ₂ and CH ₄ /N ₂ Separation in Zeolites and Metal−Organic Frameworks Liu, Bei; Smit, Berend Langmuir, Vol. 25, Issue 10 https://doi.org/10.1021/la900823d	journal	May 2009
Thermosensitive gating effect and selective gas adsorption in a porous coordination nanocage Zhao, Dan; Yuan, Daqiang; Krishna, Rajamani Chemical Communications, Vol. 46, Issue 39 https://doi.org/10.1039/c0cc02771e	journal	January 2010
Hydrogen Sieving and Storage in Fullerene Intercalated Graphite Kuc, Agnieszka; Zhechkov, Lyuben; Patchkovskii, Serguei Nano Letters, Vol. 7, Issue 1 https://doi.org/10.1021/nl0619148	journal	January 2007
Internal Energy Effects in Mass Spectrometry Vékey, Károly Journal of Mass Spectrometry, Vol. 31, Issue 5 https://doi.org/10.1002/(sici)1096-9888(199605)31:5<445::aid-jms354>3.0.co;2-g	journal	May 1996
Determination of the thermal energy and its distribution in peptides Drahos, László; Vékey, Károly Journal of the American Society for Mass Spectrometry, Vol. 10, Issue 4 https://doi.org/10.1016/s1044-0305(98)00156-1	journal	April 1999
Comment on Comparative Molecular Simulation Study of CO₂/N₂ and CH₄/N₂ Separation in Zeolites and Metal−Organic Frameworks Krishna, Rajamani; van Baten, Jasper M. Langmuir, Vol. 26, Issue 4 https://doi.org/10.1021/la9041875	journal	December 2009

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