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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. doi: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. doi: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. doi: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 referencing / citing this record:

Self-adjusting binding pockets enhance H 2 and CH 4 adsorption in a uranium-based metal–organic framework
journal, January 2020

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