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Epoxidation of Ethylene by Silver Oxide (Ag2O) Cluster: A Density Functional Theory Study

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Abstract

Density functional theory (DFT) calculations were employed to study epoxidation of ethylene on a [Ag14O9] cluster model representing silver oxide (001) surface. Theoretical results obtained in this study showed that formation paths of acetaldehyde and vinyl alcohol have higher activation barriers than that of ethylene oxide formation path on silver oxide (35 and 35 vs. 20 kcal/mol). Formation of the ethylene oxometallocycle intermediate is found to have a low probability on Ag2O(001) surface. The essential reason for this may be lower basicity of surface oxygen atom on silver oxide surface and the absence of a surface vacancy position to activate ethylene. Adsorbed EO is formed on Ag2O surface cluster without an activation barrier. The activation barriers of the rate-limiting steps for the production of EO mechanisms (via ethyleneoxy and non-activated paths, 20 vs. 14 kcal/mol) are in relatively good agreement with the experimental activation energy values (14, 17 and 22 kcal/mol) reported for EO formation on silver catalyst.

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Acknowledgments

This research was supported in part by TÜBİTAK through TR-Grid e-Infrastructure Project. TR-Grid systems are hosted by TÜBİTAK ULAKBİM and Middle East Technical University. Visit http://www.grid.org.tr for more information. This study was also supported by CENG HPC System of METU.

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Author notes

  1. Mehmet Ferdi Fellah

    Present address: Department of Chemical Engineering, Yuzuncu Yil University, Van, 65080, Turkey

Authors and Affiliations

  1. Department of Chemical Engineering, Middle East Technical University, Ankara, 06531, Turkey

    Mehmet Ferdi Fellah & Isik Onal

  2. Schuit Institute of Catalysis, Eindhoven University of Technology, P.O. Box 513, 5600 MB, Eindhoven, The Netherlands

    Rutger A. van Santen

Authors
  1. Mehmet Ferdi Fellah
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  2. Rutger A. van Santen
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  3. Isik Onal
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Correspondence to Mehmet Ferdi Fellah, Rutger A. van Santen or Isik Onal.

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Fellah, M.F., van Santen, R.A. & Onal, I. Epoxidation of Ethylene by Silver Oxide (Ag2O) Cluster: A Density Functional Theory Study. Catal Lett 141, 762–771 (2011). https://doi.org/10.1007/s10562-011-0614-2

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  • DOI: https://doi.org/10.1007/s10562-011-0614-2

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