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Direct synthesis of dimethyl carbonate from CO2 and methanol over CeO2 catalysts of different morphologies

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Abstract

The direct synthesis of dimethyl carbonate (DMC) from carbon dioxide (CO2) and methanol is an attractive approach towards conversion of the greenhouse gas - CO2 into value-added chemicals and fuels. Ceria (CeO2) catalyzes this reaction. But the conversion efficiency of CeO2 is enhanced when the byproduct water in the reaction medium is separated by employing trapping agents like 2-cyanopyridine (2-CP). In this work, the influence of morphology of CeO2 on the direct synthesis of DMC in presence of 2-CP is reported. CeO2 catalysts of cube, rod, spindle and irregular morphology (Ce - C, Ce - R, Ce - S and Ce - N, respectively) were prepared, characterized and studied as catalysts in the said reaction conducted in a batch mode. Among all, Ce - S shows superior catalytic performance with nearly 100 mol% of DMC selectivity. Catalytic activity correlates with the concentration of acid and base sites of medium strength as well as defect sites. Ce - S has an optimum number of these active sites and thereby shows superior catalytic performance.

Direct synthesis of dimethyl carbonate from CO2 and methanol in presence of 2-cyanopyridine as water trapping agent was studied with CeO2 of different morphologies as a catalyst. Catalytic activity correlates with the amount of acid/base sites of medium strength, defect sites and exposed (111) facets. CeO2 with spindle morphology shows superior catalytic performance compared to rod, cube and irregular or ‘no-definite’ shape morphologies.

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Acknowledgements

P.U. acknowledges CSIR, New Delhi for the fellowship. This work forms a part of the Project “TapCoal (CSC 0102)” sponsored by CSIR.

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Authors and Affiliations

  1. Catalysis and Inorganic Chemistry Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune, 411 008, India

    UNNIKRISHNAN P & SRINIVAS DARBHA

  2. Academy of Scientific and Innovative Research (AcSIR), New Delhi, India

    UNNIKRISHNAN P & SRINIVAS DARBHA

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  1. UNNIKRISHNAN P
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Correspondence to SRINIVAS DARBHA.

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Supplementary Information (SI)

HRTEM images of Ce - N sample and catalytic activity data of Ce - S as a function of reaction temperature and reaction time are available as supporting information on the website of Journal of Chemical Sciences at www.ias.ac.in/chemsci.

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P, U., DARBHA, S. Direct synthesis of dimethyl carbonate from CO2 and methanol over CeO2 catalysts of different morphologies. J Chem Sci 128, 957–965 (2016). https://doi.org/10.1007/s12039-016-1094-0

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  • DOI: https://doi.org/10.1007/s12039-016-1094-0

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