Water reactivity with tungsten oxides: H 2 production and kinetic traps

Nicholas J. Mayhall, David W. Rothgeb, Ekram Hossain, Caroline Chick Jarrold, Krishnan Raghavachari

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    41 Scopus citations


    In a recent mass spectrometry/photoelectron spectroscopy study on the reactions between W 2 O y - (y=2-6) and water, Jarrold and co-workers [J. Chem. Phys. 130, 124314 (2009)] observed interesting differences in the reactivity of the different cluster ions. Particularly noteworthy is the observation that the only product with the incorporation of hydrogens is a single peak corresponding to W 2 O 6 H 2 -. As reactions between metal oxide clusters and small molecules such as water have high potential for catalytic applications, we carried out a careful study to obtain a mechanistic understanding of this observed reactivity. Using electronic structure calculations, we identified and characterized multiple modes of reactivity between unsaturated tungsten oxide clusters [W 2 O y - (y=4-6)] and water. By calculating the free energy corrected reaction profiles, our results provide an explanation for the formation of W 2 O 6 H 2 -. We propose a mechanism in which water reacts with a metal oxide cluster and eliminates H 2. The results from our calculations show that this is nearly a barrierless process for all suboxide clusters with the exception of W 2 O 5 -.

    Original languageEnglish (US)
    Article number144302
    JournalJournal of Chemical Physics
    Issue number14
    StatePublished - 2009

    ASJC Scopus subject areas

    • Physics and Astronomy(all)
    • Physical and Theoretical Chemistry


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