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Inverse relation of dimensionality and catalytic activity in CO2 transformation: A systematic investigation by comparing multidimensional metal-organic frameworks

Abstract

The correlation between dimensionality and active sites on deciding the catalytic performance of an MOF catalyst in CO2-epoxide cycloaddition reactions has been studied. Seven In(III) based MOFs built from carboxylic and N-donor ligands, possessing different dimensionalities and distinct coordination environments were chosen as solid acid catalysts for this study. The origin of catalytic activity of In3+/TBAB bifunctional system in CO2-PO reaction was studied in detail by performing density functional theory (DFT) calculations at the M06/LACVP**++ level. The energy barrier of the propylene oxide ring opening in the presence of In3+/Br- is 11.5 kcal/mol, which is significantly lower than that of un-catalyzed (55-63 kcal/mol) and Br--catalyzed (19.5 kcal/mol) reactions, which confirms the importance of In3+/Br- binary catalytic system in the CO2-epoxide cycloaddition reactions. The one-dimensional (1D) MOF with unsaturated metal centers exhibited higher catalytic activity (PO conversion: 91%, temperature: 50 °C, time: 12 h) than the two- and three-dimensional MOFs. The role of dimensionality and unsaturated metal centers in cycloaddition reactions were explained on the basis of the results of activity testing and structural investigations. In addition, a plausible reaction mechanism for the catalytic activity of 1D MOF was proposed with reference to our structure-density functional theory correlations.

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Publication details

The article was received on 09 May 2017, accepted on 10 Jul 2017 and first published on 11 Jul 2017


Article type: Paper
DOI: 10.1039/C7TA04004K
Citation: J. Mater. Chem. A, 2017, Accepted Manuscript
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    Inverse relation of dimensionality and catalytic activity in CO2 transformation: A systematic investigation by comparing multidimensional metal-organic frameworks

    R. Babu, R. K. Roshan, Y. Gim, Y. H. Jang, J. F. Kurisingal, D. Kim and D. Park, J. Mater. Chem. A, 2017, Accepted Manuscript , DOI: 10.1039/C7TA04004K

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