First principles Monte Carlo simulations of unary and binary adsorption: CO2, N2, and H2O in Mg-MOF-74

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, we report first...

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Bibliographic Details
Published in:Chemical communications (Cambridge, England) England), 2018, Vol.54 (77), p.10816-10819
Main Authors: Fetisov, Evgenii O, Shah, Mansi S, Long, Jeffrey R, Tsapatsis, Michael, Siepmann, J Ilja
Format: Article
Language:English
Subjects:
Adsorbates
Adsorption
Carbon dioxide
Chemical bonds
Computer simulation
Electron density
First principles
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Metal-organic frameworks
Monte Carlo simulation
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Summary: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, 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. 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.
ISSN:1359-7345
1364-548X
DOI:10.1039/c8cc06178e