Chemical principles of the sulfidation of tungsten oxides

A.J. Vlies, van der, R. Prins, T. Weber

    Research output: Contribution to journalArticleAcademicpeer-review

    34 Citations (Scopus)

    Abstract

    The sulfidation of crystalline m-WO3 and WO3•H2O and the thermal decomposition of (NH4)2WO2S2 to an {WOS2} oxysulfide were studied by means of X-ray powder diffraction, quick extended X-ray absorption fine structure, and infrared emission spectroscopy. Several of the basic steps in the sulfidation reactions of m-WO3 and WO3•H2O were resolved and explained in terms of the structures of the oxides. In both cases, the sulfidation reaction follows the same general route, starting at low temperatures with the reduction of the crystalline oxides by H2S to give hydrogen tungsten bronzes. Only after this reduction can sulfur be incorporated into the oxide structure. At higher temperatures the hydrogen tungsten bronzes transform into shear oxides. Oxygen-sulfur exchange processes on the surface proceed at a higher rate, and shear oxysulfide phases form. Further incorporation of sulfur leads to oxysulfide intermediates with higher S:W ratios. W-S redox reactions eventually transform the oxysulfidic phase into WS2.
    Original languageEnglish
    Pages (from-to)9277-9285
    Number of pages9
    JournalJournal of Physical Chemistry B
    Volume106
    Issue number36
    DOIs
    Publication statusPublished - 2002

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