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Surface Reactivity of the Vanadium Phosphate Catalyst for the Oxidation of Methane

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Abstract

Using density functional theory (DFT), we compared the reactivity of vanadyl pyrophosphate (VPP) (100), α-VOPO4 (100), and δ-VOPO4 (100) for key elementary steps of the transformation of methane, serving also as model for similar steps that might occur for other hydrocarbon species. We examined in analogous fashion the initial and rate-determining homolytic C–H cleavage and the reaction of methoxy species to methanol. According to these calculated results, the system prefers the oxidation state V3+ for both types of reactions, thus avoiding the unstable oxidation state V2+. On the three surfaces modelled, either bare or hydrogenated, the models indicate a rather similar reactivity for C–H cleavage whereas methoxy species are energetically preferred over methanol.

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Acknowledgements

T.F. thanks Shrabani Dinda, Velina Markova, Weina Zhao, and Bimal Pudasaini for helpful discussions. We acknowledge generous computing resources at the National Supercomputing Centre Singapore and the A*STAR Computational Resource Centre.

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Authors and Affiliations

  1. Agency for Science, Technology and Research, Institute of High Performance Computing, 1 Fusionopolis Way, #16-16 Connexis, Singapore, 138632, Singapore

    Torstein Fjermestad, Alexander Genest, Wenqing Li & Notker Rösch

  2. Clariant Produkte (Deutschland) GmbH, Waldheimer Str. 13, 83052, Heufeld, Germany

    Gerhard Mestl

  3. Department Chemie and Catalysis Research Center, Technische Universität München, 85747, Garching, Germany

    Notker Rösch

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  1. Torstein Fjermestad
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  2. Alexander Genest
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  5. Notker Rösch
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Correspondence to Notker Rösch.

Additional information

The authors dedicate this work to the memory of the late Professor Helmut Knözinger. He provided invaluable mentorship to both senior authors, by guiding G.M. through is Ph.D. research and by introducing N.R. to the surface science of oxide materials.

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Fjermestad, T., Genest, A., Li, W. et al. Surface Reactivity of the Vanadium Phosphate Catalyst for the Oxidation of Methane. Top Catal 60, 1698–1708 (2017). https://doi.org/10.1007/s11244-017-0848-3

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