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Title: First principles Monte Carlo simulations of unary and binary adsorption: CO 2, N 2, and H 2O in Mg-MOF-74

Abstract

Dative bonding of adsorbate molecules onto coordinatively-unsaturated metal sites in metal–organic frameworks can lead to unique adsorption selectivities. However, the distortion of the electron density during dative bonding poses a challenge for force-field-based simulations. Here in this paper, we report first principles Monte Carlo simulations with the PBE-D3 functional for the adsorption of CO 2, N 2, and H 2O in Mg-MOF-74, and obtain accurate predictions of the unary isotherms without any of the adjustments or fitting often required for systems with strong adsorption sites. Lastly, simulations of binary CO 2/N 2 and H 2O/CO 2 mixtures yield selectivities of 200 and 160, respectively, and indicate that predictions from ideal adsorbed solution theory need to be viewed with caution.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [2]
  1. Univ. of Minnesota, Minneapolis, MN (United States). Department of Chemistry and Chemical Theory Center
  2. Univ. of Minnesota, Minneapolis, MN (United States). Department of Chemistry and Chemical Theory Center and Department of Chemical Engineering and Materials Science
  3. Univ. of California, Berkeley, CA (United States). Department of Chemistry and Chemical & Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  4. Univ. of Minnesota, Minneapolis, MN (United States). Department of Chemical Engineering and Materials Science
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States). Nanoporous Materials Genome Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Org.:
Argonne Leadership Computing Facility; Minnesota Supercomputing Institute
OSTI Identifier:
1477218
Alternate Identifier(s):
OSTI ID: 1467129
Grant/Contract Number:  
SC0008688; FG02-17ER16362; AC02-06CH11357; De-AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ChemComm
Additional Journal Information:
Journal Volume: 54; Journal Issue: 77; Journal ID: ISSN 1359-7345
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Fetisov, Evgenii O., Shah, Mansi S., Long, Jeffrey R., Tsapatsis, Michael, and Siepmann, J. Ilja. First principles Monte Carlo simulations of unary and binary adsorption: CO2, N2, and H2O in Mg-MOF-74. United States: N. p., 2018. Web. doi:10.1039/C8CC06178E.
Fetisov, Evgenii O., Shah, Mansi S., Long, Jeffrey R., Tsapatsis, Michael, & Siepmann, J. Ilja. First principles Monte Carlo simulations of unary and binary adsorption: CO2, N2, and H2O in Mg-MOF-74. United States. doi:10.1039/C8CC06178E.
Fetisov, Evgenii O., Shah, Mansi S., Long, Jeffrey R., Tsapatsis, Michael, and Siepmann, J. Ilja. Fri . "First principles Monte Carlo simulations of unary and binary adsorption: CO2, N2, and H2O in Mg-MOF-74". United States. doi:10.1039/C8CC06178E.
@article{osti_1477218,
title = {First principles Monte Carlo simulations of unary and binary adsorption: CO2, N2, and H2O in Mg-MOF-74},
author = {Fetisov, Evgenii O. and Shah, Mansi S. and Long, Jeffrey R. and Tsapatsis, Michael and Siepmann, J. Ilja},
abstractNote = {Dative bonding of adsorbate molecules onto coordinatively-unsaturated metal sites in metal–organic frameworks can lead to unique adsorption selectivities. However, the distortion of the electron density during dative bonding poses a challenge for force-field-based simulations. Here in this paper, we report first principles Monte Carlo simulations with the PBE-D3 functional for the adsorption of CO2, N2, and H2O in Mg-MOF-74, and obtain accurate predictions of the unary isotherms without any of the adjustments or fitting often required for systems with strong adsorption sites. Lastly, simulations of binary CO2/N2 and H2O/CO2 mixtures yield selectivities of 200 and 160, respectively, and indicate that predictions from ideal adsorbed solution theory need to be viewed with caution.},
doi = {10.1039/C8CC06178E},
journal = {ChemComm},
number = 77,
volume = 54,
place = {United States},
year = {Fri Aug 17 00:00:00 EDT 2018},
month = {Fri Aug 17 00:00:00 EDT 2018}
}

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