Accurate model for predicting adsorption of olefins and paraffins on MOFs with open metal sites

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Jorge, Miguel and Fischer, Michael and Gomes, Jose R. B. and Siquet, Christophe and Santos, João C and Rodrigues, Alirio E. (2014) Accurate model for predicting adsorption of olefins and paraffins on MOFs with open metal sites. Industrial and Engineering Chemistry Research. ISSN 0888-5885 (https://doi.org/10.1021/ie500310c)

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Abstract

Metal–organic frameworks (MOFs) have shown tremendous potential for challenging gas separation applications, an example of which is the separation of olefins from paraffins. Some of the most promising MOFs show enhanced selectivity for the olefins due to the presence of coordinatively unsaturated metal sites, but accurate predictive models for such systems are still lacking. In this paper, we present results of a combined experimental and theoretical study on adsorption of propane, propylene, ethane, and ethylene in CuBTC, a MOF with open metal sites. We first propose a simple procedure to correct for impurities present in real materials, which in most cases makes experimental data from different sources consistent with each other and with molecular simulation results. By applying a novel molecular modeling approach based on a combination of quantum mechanical density functional theory and classical grand canonical Monte Carlo simulations, we are able to achieve excellent predictions of olefin adsorption, in much better agreement with experiment than traditional, mostly empirical, molecular models. Such an improvement in predictive ability relies on a correct representation of the attractive energy of the unsaturated metal for the carbon–carbon double bond present in alkenes. This approach has the potential to be generally applicable to other gas separations that involve specific coordination-type bonds between adsorbates and adsorbents.

ORCID iDs

Jorge, Miguel ORCID logoORCID: https://orcid.org/0000-0003-3009-4725, Fischer, Michael, Gomes, Jose R. B., Siquet, Christophe, Santos, João C and Rodrigues, Alirio E.;
  • Item type:Article
    ID code:47881
    Dates:
    Date
    Event
    2014
    Published
    11 March 2014
    Published Online
    11 March 2014
    Accepted
    Notes:This document is the unedited author's version of a Submitted Work that was subsequently accepted for publication in Industrial and Engineering Chemistry Research, copyright © American Chemical Society after peer review. To access the final edited and published work, see http://dx.doi.org/10.1021/ie500310c
    Subjects:Science > Chemistry
    Technology > Chemical engineering
    Department:Faculty of Engineering > Chemical and Process Engineering
    Depositing user: Pure Administrator
    Date deposited:07 May 2014 12:43
    Last modified:20 Dec 2024 01:20
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/47881
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