The Mechanism of CO and CO2 Hydrogenation to Methanol over Cu-Based Catalysts

Authors

  • Dr. Felix Studt,

    Corresponding author
    1. SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA 94025 (USA)
    2. Department of Chemical Engineering, Stanford University, Stanford, CA 94305 (USA)
    • Felix Studt, SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA 94025 (USA)

      Malte Behrens, Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4–6, 14195 Berlin (Germany)

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    • These authors contributed equally to this work.

  • Prof. Malte Behrens,

    Corresponding author
    1. Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4–6, 14195 Berlin (Germany)
    2. Faculty of Chemistry and CENIDE, Universität Duisburg-Essen, Universitätsstrasse 5–7, 45141 Essen (Germany)
    • Felix Studt, SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA 94025 (USA)

      Malte Behrens, Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4–6, 14195 Berlin (Germany)

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    • These authors contributed equally to this work.

  • Dr. Edward L. Kunkes,

    1. Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4–6, 14195 Berlin (Germany)
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  • Dr. Nygil Thomas,

    1. Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4–6, 14195 Berlin (Germany)
    2. Present address: Postgraduate and Research Department of Chemistry, Nirmalagiri College, Kerala, India
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  • Dr. Stefan Zander,

    1. Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4–6, 14195 Berlin (Germany)
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  • Dr. Andrey Tarasov,

    1. Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4–6, 14195 Berlin (Germany)
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  • Julia Schumann,

    1. Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4–6, 14195 Berlin (Germany)
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  • Dr. Elias Frei,

    1. Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4–6, 14195 Berlin (Germany)
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  • Dr. Joel B. Varley,

    1. Department of Chemical Engineering, Stanford University, Stanford, CA 94305 (USA)
    2. Lawrence Livermore National Laboratory, Livermore, CA 94550 (USA)
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  • Dr. Frank Abild-Pedersen,

    1. SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA 94025 (USA)
    2. Department of Chemical Engineering, Stanford University, Stanford, CA 94305 (USA)
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  • Prof. Jens K. Nørskov,

    1. SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA 94025 (USA)
    2. Department of Chemical Engineering, Stanford University, Stanford, CA 94305 (USA)
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  • Prof. Robert Schlögl

    1. Department of Inorganic Chemistry, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4–6, 14195 Berlin (Germany)
    2. Heterogeneous Reactions Department, Max-Planck-Institut for Chemical Energy Conversion, Stiftstrasse 34–36, 45470 Mühlheim an der Ruhr (Germany)
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Abstract

Methanol, an important chemical, fuel additive, and precursor for clean fuels, is produced by hydrogenation of carbon oxides over Cu-based catalysts. Despite the technological maturity of this process, the understanding of this apparently simple reaction is still incomplete with regard to the reaction mechanism and the active sites. Regarding the latter, recent progress has shown that stepped and ZnOx-decorated Cu surfaces are crucial for the performance of industrial catalysts. Herein, we integrate this insight with additional experiments into a full microkinetic description of methanol synthesis. In particular, we show how the presence or absence of the Zn promoter dramatically changes not only the activity, but unexpectedly the reaction mechanism itself. The Janus-faced character of Cu with two different sites for methanol synthesis, Zn-promoted and unpromoted, resolves the long-standing controversy regarding the Cu/Zn synergy and adds methanol synthesis to the few major industrial catalytic processes that are described on an atomic level.

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