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Theoretical study of the effect of halogen substitution in molecular porous materials for CO2 and C2H2 sorption

Department of Chemistry, University of South Florida, 4202 East Fowler Avenue, CHE205, Tampa,FL 33620-5250, USA

Special Issue: Synthesis and Applications of Metal-Organic Frameworks (MOFs)

Grand canonical Monte Carlo (GCMC) simulations of carbondioxide (CO$_2$) and acetylene (C$_2$H$_2$) sorption were performed inMPM-1-Cl and MPM-1-Br, two robust molecular porous materials (MPMs) thatwere synthesized by the addition of adenine to CuX$_2$ (X = Cl or Br)by solvent diffusion. Previous experimental studies revealed that bothMPMs are selective for C$_2$H$_2$ over CO$_2$ [Xie DY, et al. (2017) ${CIESC J}$ 68: 154--162]. Simulations in MPM-1-Cl and MPM-1-Br werecarried out using polarizable and nonpolarizable potentials of therespective sorbates; this was done to investigate the role of explicitinduction on the gas sorption mechanism in these materials. The calculatedsorption isotherms and isosteric heat of adsorption ($Q_{st}$) valuesfor both sorbates are in reasonable agreement with the correspondingexperimental measurements, with simulations using the polarizable modelsproducing the closest overall agreement. The modeled CO$_2$ binding sitein both MPMs was discovered as sorption between the halide ions oftwo adjacent [Cu$_2$(adenine)$_4$X$_2$]$^{2+}$ (X = Cl, Br) units.In the case of C$_2$H$_2$, it was found that the sorbate molecule prefersto align along the X--Cu--Cu--X axis of the copper paddlewheels suchthat each H atom of the C$_2$H$_2$ molecule can interact favorably withthe coordinated X$^-$ ions. The simulations revealed that both MPMsexhibit stronger interactions with C$_2$H$_2$ than CO$_2$, which isconsistent with experimental findings. The effect of halogen substitutiontoward CO$_2$ and C$_2$H$_2$ sorption in two isostructural MPMs wasalso elucidated in our theoretical studies.
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Keywords metal–organic framework; simulation; gas sorption; carbon dioxide; acetylene; gas separation

Citation: Douglas M. Franz, Mak Djulbegovic, Tony Pham, Brian Space. Theoretical study of the effect of halogen substitution in molecular porous materials for CO2 and C2H2 sorption. AIMS Materials Science, 2018, 5(2): 226-245. doi: 10.3934/matersci.2018.2.226


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