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Methanol Adsorption on V2O3(0001)

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Abstract

Well ordered V2O3(0001) layers may be grown on Au(111) surfaces. These films are terminated by a layer of vanadyl groups which may be removed by irradiation with electrons, leading to a surface terminated by vanadium atoms. We present a study of methanol adsorption on vanadyl terminated and vanadium terminated surfaces as well as on weakly reduced surfaces with a limited density of vanadyl oxygen vacancies produced by electron irradiation. Different experimental methods and density functional theory are employed. For vanadyl terminated V2O3(0001) only molecular methanol adsorption was found to occur whereas methanol reacts to form formaldehyde, methane, and water on vanadium terminated and on weakly reduced V2O3(0001). In both cases a methoxy intermediate was detected on the surface. For weakly reduced surfaces it could be shown that the density of methoxy groups formed after methanol adsorption at low temperature is twice as high as the density of electron induced vanadyl oxygen vacancies on the surface which we attribute to the formation of additional vacancies via the reaction of hydroxy groups to form water which desorbs below room temperature. Density functional theory confirms this picture and identifies a methanol mediated hydrogen transfer path as being responsible for the formation of surface hydroxy groups and water. At higher temperature the methoxy groups react to form methane, formaldehyde, and some more water. The methane formation reaction consumes hydrogen atoms split off from methoxy groups in the course of the formaldehyde production process as well as hydrogen atoms still being on the surface after being produced at low temperature in the course of the methanol → methoxy + H reaction.

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Acknowledgements

This work was funded by the Deutsche Forschungsgemeinschaft through their Sonderforschungsbereich 546 ‘Transition Metal Oxide Aggregates’. The Fonds der Chemischen Industrie is gratefully acknowledged for financial support. We acknowledge the Helmholtz-Zentrum Berlin—Electron storage ring BESSY II for provision of synchrotron radiation at beamline UE52-PGM.

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Author notes

  1. J. M. Sturm

    Present address: FOM-Institute for Plasma Physics Rijnhuizen, Postbus 1207, 3430 BE, Nieuwegein, The Netherlands

  2. J. Döbler

    Present address: Computer and Media Services, Humbold-Universität zu Berlin, Unter den Linden 6, 10099, Berlin, Germany

  3. M. V. Ganduglia-Pirovano

    Present address: Institute of Catalysis and Petrochemistry of the Spanish National Research Council, Marie Curie 2, 28049, Madrid, Spain

  4. S. Guimond

    Present address: Empa, Swiss Federal Laboratories for Materials Science and Technology, Lerchenfeldstr. 5, 9014, St. Gallen, Switzerland

Authors and Affiliations

  1. Chemical Physics Department, Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195, Berlin, Germany

    Y. Romanyshyn, S. Guimond, D. Göbke, J. M. Sturm, H. Kuhlenbeck & H.-J. Freund

  2. Department of Chemistry, Humbold-Universität zu Berlin, Unter den Linden 6, 10099, Berlin, Germany

    J. Döbler, M. V. Ganduglia-Pirovano & J. Sauer

Authors
  1. Y. Romanyshyn
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  2. S. Guimond
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  8. J. Sauer
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  9. H.-J. Freund
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Corresponding author

Correspondence to H. Kuhlenbeck.

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Dedicated to Professor Robert K. Grasselli on the occasion of his 80th birthday

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Romanyshyn, Y., Guimond, S., Göbke, D. et al. Methanol Adsorption on V2O3(0001). Top Catal 54, 669–684 (2011). https://doi.org/10.1007/s11244-011-9685-y

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