Modeling Adsorption in Metal-Organic Frameworks with Open Metal Sites: Propane/Propylene Separations
authors Fischer, M; Gomes, JRB; Froba, M; Jorge, M
nationality International
journal LANGMUIR
keywords GENERALIZED-GRADIENT-APPROXIMATION; UNITED-ATOM DESCRIPTION; MOLECULAR SIMULATION; FORCE-FIELD; TRANSFERABLE POTENTIALS; HYDROGEN ADSORPTION; ACETYLENE STORAGE; PHASE-EQUILIBRIA; POROUS MATERIALS; METHANE STORAGE
abstract We present a new approach for modeling adsorption in metal-organic frameworks (MOFs) with unsaturated metal centers and apply it to the challenging propane/propylene separation in copper(II) benzene-1,3,5-tricarboxylate (CuBTC). We obtain information about the specific interactions between olefins and the open metal sites of the MOP using quantum mechanical density functional theory. A proper consideration of all the relevant contributions to the adsorption energy enables us to extract the component that is due to specific attractive interactions between the pi-orbitals of the alkene and the coordinatively unsaturated metal. This component is fitted using a combination of a Morse potential and a power law function and is then included into classical grand canonical Monte Carlo simulations of adsorption. Using this modified potential model, together with a standard Lennard-Jones model, we are able to predict the adsorption of not only propane (where no specific interactions are present), but also of propylene (where specific interactions are dominant). Binary adsorption isotherms for this mixture are in reasonable agreement with ideal adsorbed solution theory predictions. We compare our approach with previous attempts to predict adsorption in MOFs with open metal sites and suggest possible future routes for improving our model.
publisher AMER CHEMICAL SOC
issn 0743-7463
year published 2012
volume 28
issue 22
beginning page 8537
ending page 8549
digital object identifier (doi) 10.1021/la301215y
web of science category Chemistry, Multidisciplinary; Chemistry, Physical; Materials Science, Multidisciplinary
subject category Chemistry; Materials Science
unique article identifier WOS:000304783300031
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journal impact factor 3.557
5 year journal impact factor 3.702
category normalized journal impact factor percentile 64.177
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