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Methanol synthesis and reverse water-gas shift kinetics over clean polycrystalline copper

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Abstract

The kinetics of simultaneous methanol synthesis and reverse water-gas shift from CO2/H2 mixtures have been measured at low conversions over a clean polycrystalline Cu foil at pressures of 5 bar. An absolute rate of 1.2 × 10−3 methanol molecules produced per second per Cu surface atom was observed at 510 K, with an activation energy of 77 ± 10 kJ/mol. The rate of CO production was 0.12 molecules per second per Cu surface atom at this temperature, with an activation energy of 135 ± 5 kJ/mol. The rates, normalized to the metallic Cu surface area, are equal to those measured over real, high-area Cu/ZnO catalysts. The surface after reaction was examined by XPS and TPD. It was covered by almost a full monolayer of adsorbed formate, but no other species like carbon or oxygen in measurable amounts. These results prove that a highly active site for methanol synthesis on real Cu/ZnO catalysts is metallic Cu, and suggest that the rate-determining step in methanol synthesis is one of the several steps in the further hydrogenation of adsorbed formate to methanol.

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  1. Department of Chemistry, University of Washington, 98195, Seattle, WA, USA

    Jun Yoshihara, S. C. Parker, Adam Schafer & Charles T. Campbell

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  1. Jun Yoshihara
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  2. S. C. Parker
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Yoshihara, J., Parker, S.C., Schafer, A. et al. Methanol synthesis and reverse water-gas shift kinetics over clean polycrystalline copper. Catal Lett 31, 313–324 (1995). https://doi.org/10.1007/BF00808595

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