Cation characterization and CO2 capture in Li+-exchanged metal-organic frameworks: From first-principles modeling to molecular simulation

Babarao, R and Jianwen, J 2011, 'Cation characterization and CO2 capture in Li+-exchanged metal-organic frameworks: From first-principles modeling to molecular simulation', Industrial and Engineering Chemistry Research, vol. 50, no. 1, pp. 62-68.


Document type: Journal Article
Collection: Journal Articles

Title Cation characterization and CO2 capture in Li+-exchanged metal-organic frameworks: From first-principles modeling to molecular simulation
Author(s) Babarao, R
Jianwen, J
Year 2011
Journal name Industrial and Engineering Chemistry Research
Volume number 50
Issue number 1
Start page 62
End page 68
Total pages 7
Publisher American Chemical Society
Abstract We report a computational study for cation characterization and CO2 capture in Li+-exchanged metal-organic frameworks (Li+-MOFs). Density functional theory is adopted to optimize cation locations and evaluate atomic charges, and molecular simulation is subsequently used to examine the separation of CO2/H2 and CO2/N2 mixtures for pre- and post-combustion CO2 capture. The cations are observed to locate near the carboxylic O-donors of metal clusters. Specifically, H+ ions in dehydrated Li+-MOF form covalent bonds with the O-donors, and H3O+ ions in hydrated Li+-MOF form hydrogen bonds with the O-donors. CO2 is overwhelmingly adsorbed over H2 and N2 in both dehydrated and hydrated Li+-MOFs. Adsorption occurs preferentially near the cations and metal clusters, which possess strong electrostatic potentials, and then in the square channels. At ambient condition, the selectivity is approximately 550 for CO2/H2 mixture and 60 for CO2/N2 mixture, higher than that in nonionic MOFs and other nanoporous adsorbents. The charges of framework and cations have a significant effect on the selectivity, which is found to decrease by 1 order of magnitude by switching off the charges. The hydration of cations in Li+-MOF leads to a reduced free volume and consequently a lower extent of adsorption.
Subject Condensed Matter Modelling and Density Functional Theory
Chemical Thermodynamics and Energetics
Theory and Design of Materials
Composite and Hybrid Materials
DOI - identifier 10.1021/ie100214a
Copyright notice © 2011 American Chemical Society
ISSN 0888-5885
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