Study of the Chemical Mechanism Involved in the Formation of Tungstite in Benzyl Alcohol by the Advanced QEXAFS Technique

Authors

  • Inga Olliges-Stadler,

    1. Laboratory for Multifunctional Materials, Department of Materials, ETH Zürich, Wolfgang-Pauli-Strasse 10, 8093 Zürich (Switzerland)
    Search for more papers by this author
  • Jan Stötzel,

    1. Department of Physics, University of Wuppertal, Gaussstrasse 20, 42097 Wuppertal (Germany)
    Search for more papers by this author
  • Dr. Dorota Koziej,

    1. Laboratory for Multifunctional Materials, Department of Materials, ETH Zürich, Wolfgang-Pauli-Strasse 10, 8093 Zürich (Switzerland)
    Search for more papers by this author
  • Dr. Marta D. Rossell,

    1. Laboratory for Multifunctional Materials, Department of Materials, ETH Zürich, Wolfgang-Pauli-Strasse 10, 8093 Zürich (Switzerland)
    Search for more papers by this author
  • Prof. Dr. Jan-Dierk Grunwaldt,

    1. Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstrasse 20, 76131 Karlsruhe (Germany)
    2. Department of Chemical and Biochemical Engineering, Technical University of Denmark, 2800 Kgs. Lyngby (Denmark)
    Search for more papers by this author
  • Dr. Maarten Nachtegaal,

    1. Swiss Light Source, Paul Scherrer Institute, 5232 Villigen (Switzerland)
    Search for more papers by this author
  • Prof. Dr. Ronald Frahm,

    1. Department of Physics, University of Wuppertal, Gaussstrasse 20, 42097 Wuppertal (Germany)
    Search for more papers by this author
  • Prof. Dr. Markus Niederberger

    Corresponding author
    1. Laboratory for Multifunctional Materials, Department of Materials, ETH Zürich, Wolfgang-Pauli-Strasse 10, 8093 Zürich (Switzerland)
    • Laboratory for Multifunctional Materials, Department of Materials, ETH Zürich, Wolfgang-Pauli-Strasse 10, 8093 Zürich (Switzerland)
    Search for more papers by this author

Abstract

Insight into the complex chemical mechanism for the formation of tungstite nanoparticles obtained by the reaction of tungsten hexachloride with benzyl alcohol is presented herein. The organic and inorganic species involved in the formation of the nanoparticles were studied by time-dependent gas chromatography and X-ray diffraction as well as by time-resolved in situ X-ray absorption near-edge structure and extended X-ray absorption fine structure spectroscopy. Principal component analysis revealed two intermediates, which were identified as WCl4 and WOCl4 by using linear combination analysis. Quick-scanning extended X-ray absorption fine structure spectroscopy enabled the time-dependent evolution of the starting compound, the intermediates and the product to be monitored over the full reaction period. The reaction starts with fast chlorine substitution and partial reduction during the dissolution of the tungsten hexachloride in benzyl alcohol followed by the generation of intermediates with W[DOUBLE BOND]O double bonds and finally the construction of the W[BOND]O[BOND]W network of the tungstite structure.

Ancillary