Catalytic and Mechanistic Insights of the Low-Temperature Selective Oxidation of Methane over Cu-Promoted Fe-ZSM-5

Authors

  • Dr. Ceri Hammond,

    Corresponding author
    1. Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT (UK)
    2. Current address: Department of Chemistry and Applied Biosciences, ETH Zürich, Wolfgang-Pauli-Str. 10, 8093 Zürich (Switzerland)
    • Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT (UK)
    Search for more papers by this author
  • Dr. Robert L. Jenkins,

    1. Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT (UK)
    Search for more papers by this author
  • Dr. Nikolaos Dimitratos,

    1. Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT (UK)
    2. Current addresses: Department of Chemistry, University College London, 20 Gordon Street, WC1H 0AJ London (UK) and Research Complex at Harwell, Rutherford Appleton Laboratory, Harwell Oxford, Didcot, OX11 0FA (UK)
    Search for more papers by this author
  • Dr. Jose Antonio Lopez-Sanchez,

    1. Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT (UK)
    Search for more papers by this author
  • Dr. Mohd Hasbi ab Rahim,

    1. Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT (UK)
    Search for more papers by this author
  • Dr. Michael M. Forde,

    1. Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT (UK)
    Search for more papers by this author
  • Adam Thetford,

    1. Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT (UK)
    Search for more papers by this author
  • Dr. Damien M. Murphy,

    1. Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT (UK)
    Search for more papers by this author
  • Dr. Henk Hagen,

    1. Dow Benelux B. V., Herbert H. Dowweg 5, 4542 NM HOEK, Postbus 48, 4530 AA Terneuzen (the Netherlands)
    Search for more papers by this author
  • Dr. Eric E. Stangland,

    1. National Corporate R&D, The Dow Chemical Company, Midland, MI 48674 (USA)
    Search for more papers by this author
  • Prof. Jacob M. Moulijn,

    1. Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT (UK)
    Search for more papers by this author
  • Dr. Stuart H. Taylor,

    1. Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT (UK)
    Search for more papers by this author
  • Dr. David J. Willock,

    1. Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT (UK)
    Search for more papers by this author
  • Prof. Graham J. Hutchings

    Corresponding author
    1. Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT (UK)
    • Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT (UK)
    Search for more papers by this author

Abstract

The partial oxidation of methane to methanol presents one of the most challenging targets in catalysis. Although this is the focus of much research, until recently, approaches had proceeded at low catalytic rates (<10 h−1), not resulted in a closed catalytic cycle, or were unable to produce methanol with a reasonable selectivity. Recent research has demonstrated, however, that a system composed of an iron- and copper-containing zeolite is able to catalytically convert methane to methanol with turnover frequencies (TOFs) of over 14 000 h−1 by using H2O2 as terminal oxidant. However, the precise roles of the catalyst and the full mechanistic cycle remain unclear. We hereby report a systematic study of the kinetic parameters and mechanistic features of the process, and present a reaction network consisting of the activation of methane, the formation of an activated hydroperoxy species, and the by-production of hydroxyl radicals. The catalytic system in question results in a low-energy methane activation route, and allows selective C1-oxidation to proceed under intrinsically mild reaction conditions.

Ancillary