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

Tsivion, Ehud; Head-Gordon, Martin

doi:10.1021/acs.jpcc.7b04246

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

Journal Article · Tue May 16 00:00:00 EDT 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b04246· OSTI ID:1464148

Tsivion, Ehud ^[1];

^[2]

Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division

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.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office; National Science Foundation (NSF)

Grant/Contract Number:: AC02-05CH11231; CHE-1363342

OSTI ID:: 1464148

Journal Information:: Journal of Physical Chemistry. C, Vol. 121, Issue 22; Related Information: © 2017 American Chemical Society.; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 21 works

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

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