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Title: Methane Storage: Molecular Mechanisms Underlying Room-Temperature Adsorption in Zn4O(BDC)3 (MOF-5)

Abstract

Here, we study how the methane adsorption properties of the ionic MOF-5 are derived from the local structure of its coordinated metal-cluster. Density functional theory is used to study the adsorption process and identify the key interactions which drive it at ambient temperatures. A detailed adsorption model which represents the adsorption process is derived and used to extract thermodynamic properties from previously reported adsorption isotherms. We find that after adsorption of a single molecule to the face of the metal cluster, a nanostructured surface is formed which enables adsorption of additional CH4 molecules at reduced entropic penalty thanks to on-surface hopping motions and retention of significant translational freedom. Binding of the CH4 molecules to the MOF is dominated by electrostatic interactions with negatively charged carboxylate groups, while CH4-CH4 dispersion interactions are important only at high pressures. Last, the MOF-specific adsorption model is compared against the single-site Langmuir model.

Authors:
 [1]; ORCiD logo [2]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office; National Science Foundation (NSF)
OSTI Identifier:
1464148
Grant/Contract Number:  
AC02-05CH11231; CHE-1363342
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 22; Related Information: © 2017 American Chemical Society.; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Tsivion, Ehud, and Head-Gordon, Martin. Methane Storage: Molecular Mechanisms Underlying Room-Temperature Adsorption in Zn4O(BDC)3 (MOF-5). United States: N. p., 2017. Web. https://doi.org/10.1021/acs.jpcc.7b04246.
Tsivion, Ehud, & Head-Gordon, Martin. Methane Storage: Molecular Mechanisms Underlying Room-Temperature Adsorption in Zn4O(BDC)3 (MOF-5). United States. https://doi.org/10.1021/acs.jpcc.7b04246
Tsivion, Ehud, and Head-Gordon, Martin. Tue . "Methane Storage: Molecular Mechanisms Underlying Room-Temperature Adsorption in Zn4O(BDC)3 (MOF-5)". United States. https://doi.org/10.1021/acs.jpcc.7b04246. https://www.osti.gov/servlets/purl/1464148.
@article{osti_1464148,
title = {Methane Storage: Molecular Mechanisms Underlying Room-Temperature Adsorption in Zn4O(BDC)3 (MOF-5)},
author = {Tsivion, Ehud and Head-Gordon, Martin},
abstractNote = {Here, we study how the methane adsorption properties of the ionic MOF-5 are derived from the local structure of its coordinated metal-cluster. Density functional theory is used to study the adsorption process and identify the key interactions which drive it at ambient temperatures. A detailed adsorption model which represents the adsorption process is derived and used to extract thermodynamic properties from previously reported adsorption isotherms. We find that after adsorption of a single molecule to the face of the metal cluster, a nanostructured surface is formed which enables adsorption of additional CH4 molecules at reduced entropic penalty thanks to on-surface hopping motions and retention of significant translational freedom. Binding of the CH4 molecules to the MOF is dominated by electrostatic interactions with negatively charged carboxylate groups, while CH4-CH4 dispersion interactions are important only at high pressures. Last, the MOF-specific adsorption model is compared against the single-site Langmuir model.},
doi = {10.1021/acs.jpcc.7b04246},
journal = {Journal of Physical Chemistry. C},
number = 22,
volume = 121,
place = {United States},
year = {2017},
month = {5}
}

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Works referenced in this record:

Storage of natural gas by adsorption on activated carbon
journal, May 1992

  • Matranga, Kimberly R.; Myers, Alan L.; Glandt, Eduardo D.
  • Chemical Engineering Science, Vol. 47, Issue 7, p. 1569-1579
  • DOI: 10.1016/0009-2509(92)85005-V

Methane storage in advanced porous materials
journal, January 2012

  • Makal, Trevor A.; Li, Jian-Rong; Lu, Weigang
  • Chemical Society Reviews, Vol. 41, Issue 23
  • DOI: 10.1039/c2cs35251f

Hydrogen storage in metal–organic frameworks
journal, January 2009

  • Murray, Leslie J.; Dincă, Mircea; Long, Jeffrey R.
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1294-1314
  • DOI: 10.1039/b802256a

Industrial applications of metal–organic frameworks
journal, January 2009

  • Czaja, Alexander U.; Trukhan, Natalia; Müller, Ulrich
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1284-1293
  • DOI: 10.1039/b804680h

Methane storage in metal–organic frameworks
journal, January 2014

  • He, Yabing; Zhou, Wei; Qian, Guodong
  • Chem. Soc. Rev., Vol. 43, Issue 16
  • DOI: 10.1039/C4CS00032C

Post-synthetic metalation of metal–organic frameworks
journal, January 2014

  • Evans, Jack D.; Sumby, Christopher J.; Doonan, Christian J.
  • Chem. Soc. Rev., Vol. 43, Issue 16
  • DOI: 10.1039/C4CS00076E

Gas Adsorption Sites in a Large-Pore Metal-Organic Framework
journal, August 2005

  • Rowsell, Jesse L. C.; Spencer, Elinor C.; Eckert, Juergen
  • Science, Vol. 309, Issue 5739, p. 1350-1354
  • DOI: 10.1126/science.1113247

Self-Diffusion of Chain Molecules in the Metal–Organic Framework IRMOF-1: Simulation and Experiment
journal, March 2012

  • Ford, Denise C.; Dubbeldam, David; Snurr, Randall Q.
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 7
  • DOI: 10.1021/jz300141n

Condensation of Methane in the Metal–Organic Framework IRMOF-1: Evidence for Two Critical Points
journal, August 2015

  • Höft, Nicolas; Horbach, Jürgen
  • Journal of the American Chemical Society, Vol. 137, Issue 32
  • DOI: 10.1021/jacs.5b04077

When the Solvent Locks the Cage: Theoretical Insight into the Transmetalation of MOF-5 Lattices and Its Kinetic Limitations
journal, April 2015


Dynamic DMF Binding in MOF-5 Enables the Formation of Metastable Cobalt-Substituted MOF-5 Analogues
journal, July 2015


Design strategies for metal alkoxide functionalized metal–organic frameworks for ambient temperature hydrogen storage
journal, May 2013


Storage and Separation of CO 2 and CH 4 in Silicalite, C 168 Schwarzite, and IRMOF-1:  A Comparative Study from Monte Carlo Simulation
journal, January 2007

  • Babarao, Ravichandar; Hu, Zhongqiao; Jiang, Jianwen
  • Langmuir, Vol. 23, Issue 2
  • DOI: 10.1021/la062289p

Hydrogen and Methane Adsorption in Metal−Organic Frameworks:  A High-Pressure Volumetric Study
journal, November 2007

  • Zhou, Wei; Wu, Hui; Hartman, Michael R.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 44
  • DOI: 10.1021/jp074889i

Evaluating metal–organic frameworks for natural gas storage
journal, January 2014

  • Mason, Jarad A.; Veenstra, Mike; Long, Jeffrey R.
  • Chemical Science, Vol. 5, Issue 1, p. 32-51
  • DOI: 10.1039/C3SC52633J

Computational study of hydrogen binding by metal-organic framework-5
journal, January 2004

  • Sagara, Tatsuhiko; Klassen, James; Ganz, Eric
  • The Journal of Chemical Physics, Vol. 121, Issue 24
  • DOI: 10.1063/1.1809608

A Density Functional Theory Study of Hydrogen Adsorption in MOF-5
journal, September 2005

  • Mueller, Tim; Ceder, Gerbrand
  • The Journal of Physical Chemistry B, Vol. 109, Issue 38
  • DOI: 10.1021/jp051202q

Interaction of Hydrogen with MOF-5
journal, October 2005

  • Bordiga, Silvia; Vitillo, Jenny G.; Ricchiardi, Gabriele
  • The Journal of Physical Chemistry B, Vol. 109, Issue 39
  • DOI: 10.1021/jp052611p

Ab Initio Study of Hydrogen Adsorption in MOF-5
journal, March 2009

  • Sillar, Kaido; Hofmann, Alexander; Sauer, Joachim
  • Journal of the American Chemical Society, Vol. 131, Issue 11
  • DOI: 10.1021/ja8099079

Molecular simulation of adsorption sites of light gases in the metal-organic framework IRMOF-1
journal, December 2007


Methane Sorption in Nanoporous Metal−Organic Frameworks and First-Order Phase Transition of Confined Methane
journal, January 2009

  • Wu, Hui; Zhou, Wei; Yildirim, Taner
  • The Journal of Physical Chemistry C, Vol. 113, Issue 7
  • DOI: 10.1021/jp8103276

Recent developments in first-principles force fields for molecules in nanoporous materials
journal, January 2014

  • Fang, Hanjun; Demir, Hakan; Kamakoti, Preeti
  • J. Mater. Chem. A, Vol. 2, Issue 2
  • DOI: 10.1039/C3TA13073H

Quantum-Chemical Characterization of the Properties and Reactivities of Metal–Organic Frameworks
journal, April 2015

  • Odoh, Samuel O.; Cramer, Christopher J.; Truhlar, Donald G.
  • Chemical Reviews, Vol. 115, Issue 12
  • DOI: 10.1021/cr500551h

Ab Initio Prediction of Adsorption Isotherms for Small Molecules in Metal–Organic Frameworks: The Effect of Lateral Interactions for Methane/CPO-27-Mg
journal, September 2012

  • Sillar, Kaido; Sauer, Joachim
  • Journal of the American Chemical Society, Vol. 134, Issue 44
  • DOI: 10.1021/ja307076t

The Cambridge Structural Database: a quarter of a million crystal structures and rising
journal, May 2002


Design and synthesis of an exceptionally stable and highly porous metal-organic framework
journal, November 1999

  • Li, Hailian; Eddaoudi, Mohamed; M., O'Keeffe
  • Nature, Vol. 402, Issue 6759, p. 276-279
  • DOI: 10.1038/46248

Elucidating Negative Thermal Expansion in MOF-5
journal, September 2010

  • Lock, Nina; Wu, Yue; Christensen, Mogens
  • The Journal of Physical Chemistry C, Vol. 114, Issue 39
  • DOI: 10.1021/jp103212z

Mapping the genome of meta-generalized gradient approximation density functionals: The search for B97M-V
journal, February 2015

  • Mardirossian, Narbe; Head-Gordon, Martin
  • The Journal of Chemical Physics, Vol. 142, Issue 7
  • DOI: 10.1063/1.4907719

Nonlocal van der Waals density functional: The simpler the better
journal, December 2010

  • Vydrov, Oleg A.; Van Voorhis, Troy
  • The Journal of Chemical Physics, Vol. 133, Issue 24
  • DOI: 10.1063/1.3521275

Self-consistent molecular orbital methods. 21. Small split-valence basis sets for first-row elements
journal, January 1980

  • Binkley, J. Stephen; Pople, John A.; Hehre, Warren J.
  • Journal of the American Chemical Society, Vol. 102, Issue 3
  • DOI: 10.1021/ja00523a008

Gaussian basis sets of quadruple zeta valence quality for atoms H–Kr
journal, December 2003

  • Weigend, Florian; Furche, Filipp; Ahlrichs, Reinhart
  • The Journal of Chemical Physics, Vol. 119, Issue 24
  • DOI: 10.1063/1.1627293

Describing Noncovalent Interactions beyond the Common Approximations: How Accurate Is the “Gold Standard,” CCSD(T) at the Complete Basis Set Limit?
journal, April 2013

  • Řezáč, Jan; Hobza, Pavel
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 5
  • DOI: 10.1021/ct400057w

Accurate Description of Intermolecular Interactions Involving Ions Using Symmetry-Adapted Perturbation Theory
journal, May 2015

  • Lao, Ka Un; Schäffer, Rainer; Jansen, Georg
  • Journal of Chemical Theory and Computation, Vol. 11, Issue 6
  • DOI: 10.1021/ct5010593

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package
journal, September 2014


Natural population analysis
journal, July 1985

  • Reed, Alan E.; Weinstock, Robert B.; Weinhold, Frank
  • The Journal of Chemical Physics, Vol. 83, Issue 2
  • DOI: 10.1063/1.449486

Intermolecular interaction potentials of methane and ethylene dimers calculated with the Møller–Plesset, coupled cluster and density functional methods
journal, April 1998


Ti 3+ -, V 2+/3+ -, Cr 2+/3+ -, Mn 2+ -, and Fe 2+ -Substituted MOF-5 and Redox Reactivity in Cr- and Fe-MOF-5
journal, August 2013

  • Brozek, Carl K.; Dincă, Mircea
  • Journal of the American Chemical Society, Vol. 135, Issue 34
  • DOI: 10.1021/ja4064475

Analysis of charge transfer effects in molecular complexes based on absolutely localized molecular orbitals
journal, May 2008

  • Khaliullin, Rustam Z.; Bell, Alexis T.; Head-Gordon, Martin
  • The Journal of Chemical Physics, Vol. 128, Issue 18
  • DOI: 10.1063/1.2912041

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a

Transport Theory for Cationic Zeolites: Diffusion of Benzene in Na-Y
journal, June 1995

  • Auerbach, Scott M.; Henson, Neil J.; Cheetham, Anthony K.
  • The Journal of Physical Chemistry, Vol. 99, Issue 26
  • DOI: 10.1021/j100026a025

Mobility of Aromatic Molecules in Zeolite NaY by Molecular Dynamics Simulation
journal, January 1996

  • Klein, Harald; Fuess, Hartmut; Schrimpf, Gerhard
  • The Journal of Physical Chemistry, Vol. 100, Issue 26
  • DOI: 10.1021/jp960575b

Molecular Simulations of Zeolites: Adsorption, Diffusion, and Shape Selectivity
journal, October 2008

  • Smit, Berend; Maesen, Theo L. M.
  • Chemical Reviews, Vol. 108, Issue 10
  • DOI: 10.1021/cr8002642

Understanding CO 2 Dynamics in Metal-Organic Frameworks with Open Metal Sites
journal, March 2013

  • Lin, Li-Chiang; Kim, Jihan; Kong, Xueqian
  • Angewandte Chemie International Edition, Vol. 52, Issue 16
  • DOI: 10.1002/anie.201300446

Wobbling and Hopping: Studying Dynamics of CO 2 Adsorbed in Metal–Organic Frameworks via 17 O Solid-State NMR
journal, September 2014

  • Wang, Wei David; Lucier, Bryan E. G.; Terskikh, Victor V.
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 19
  • DOI: 10.1021/jz501729d

Understanding The Fascinating Origins of CO 2 Adsorption and Dynamics in MOFs
journal, August 2016


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    journal, January 2020

    • Halter, Dominik P.; Klein, Ryan A.; Boreen, Michael A.
    • Chemical Science
    • DOI: 10.1039/d0sc02394a

    A stable metal cluster-metalloporphyrin MOF with high capacity for cationic dye removal
    journal, January 2018

    • Wang, Zheng; Zhang, Jian-Hua; Jiang, Ji-Jun
    • Journal of Materials Chemistry A, Vol. 6, Issue 36
    • DOI: 10.1039/c8ta06249h

    MOFs-Based Heterogeneous Catalysts: New Opportunities for Energy-Related CO 2 Conversion
    journal, October 2018

    • Lei, Zhendong; Xue, Yuancheng; Chen, Wenqian
    • Advanced Energy Materials, Vol. 8, Issue 32
    • DOI: 10.1002/aenm.201801587