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Comparative Analysis of Reactant and Product Adsorption Energies in the Selective Oxidative Coupling of Alcohols to Esters on Au(111)

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Abstract

Gold-based heterogeneous catalysts have attracted significant attention due to their selective partial oxidation capabilities, providing promising alternatives for the traditional industrial homogeneous catalysts. In the current study, the energetics of adsorption/desorption of alcohols (CH3OH/methanol, CH3CH2OH/ethanol, CH3CH2CH2OH/n-propanol) and esters (HCOOCH3/methyl formate, CH3COOCH3/methyl acetate, and CH3COOCH2CH3/ethyl acetate) on a planar Au(111) surface was investigated in conjunction with oxidative coupling reactions by means of temperature programmed desorption (TPD) and dispersion-corrected density functional theory (DFT) calculations. The results reveal a complex interplay between inter-molecular and surface-molecule interactions, both mediated by weak van der Waals forces, which dictates their relative stability on the gold surface. Both experimental and theoretical adsorption/desorption energies of the investigated esters are lower than those of the alcohols from which they originate through oxidative coupling reactions. This result can be interpreted as an important indication in favor of the selectivity of Au surfaces in alcohol oxidative coupling/partial oxidation reactions, allowing facile removal of partial oxidation products immediately after their generation preventing their complete oxidation to higher oxygenates.

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Acknowledgments

E. V., M. K., A. A. S. and E. O. acknowledge financial support from the Scientific and Technological Research Council of Turkey (TÜBİTAK, Program Code: 2221 and Grant No: 112T589). H. U. and D. T. gratefully acknowledge the support by TÜBITAK Grant No. 113F099 in addition to the computational resources provided by the National Center of Academic Network and Information (TÜBITAK ULAKBIM) and the National Center for High Performance Computing (UHEM) Grant No. 5003342014.

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Authors and Affiliations

  1. Department of Physics, Middle East Technical University, Dumlupinar Bulvari 1, 06800, Ankara, Turkey

    Selma Şenozan & Hande Ustunel

  2. Department of Chemistry, Bilkent University, 06800, Bilkent, Ankara, Turkey

    Mustafa Karatok, Evgeny I. Vovk, Asad A. Shah & Emrah Ozensoy

  3. Boreskov Institute of Catalysis, Novosibirsk, Russian Federation, 630090

    Evgeny I. Vovk

  4. Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Trieste, Via L. Giorgieri 1, 34127, Trieste, Italy

    Daniele Toffoli

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  1. Selma Şenozan
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  2. Hande Ustunel
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  4. Evgeny I. Vovk
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Correspondence to Hande Ustunel or Daniele Toffoli.

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Şenozan, S., Ustunel, H., Karatok, M. et al. Comparative Analysis of Reactant and Product Adsorption Energies in the Selective Oxidative Coupling of Alcohols to Esters on Au(111). Top Catal 59, 1383–1393 (2016). https://doi.org/10.1007/s11244-016-0660-5

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