Grant Johnson - Stoichiometric zirconium oxide cations as potential building blocks for cluster assembled catalysts

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      Publication Details (including relevant citation   information):


      Volume:   130

        Issue: 42

        Pages: 13912-13920


    Published: OCT 22 2008


        Employing guided-ion-beam mass spectrometry, we identified a   series of positively charged stoichiometric zirconium oxide   clusters that exhibit enhanced activity and selectivity for three   oxidation reactions of widespread chemical importance. Density   functional theory calculations reveal that these clusters all   contain the same active site consisting of a radical oxygen   center with an elongated zirconium-oxygen bond. Calculated energy   profiles demonstrate that each oxidation reaction is highly   favorable energetically and involves easily surmountable   barriers. Furthermore, the active stoichiometric clusters may be   regenerated by reacting oxygen-deficient clusters with a strong   oxidizer. This indicates that these species may promote multiple   cycles of oxidation reactions and, therefore, exhibit true   catalytic behavior. The stoichiometric clusters, having   structures that resemble specific sites in bulk zirconia, are   promising candidates for potential incorporation into a cluster   assembled catalyst material.

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