Grant Johnson - Reactivity Trends in the Oxidation of CO by Anionic Transition Metal Oxide Clusters

Version 1

      Publication Details (including relevant citation   information):

    JOURNAL OF PHYSICAL CHEMISTRY C

      Volume:   114

        Issue: 12

        Pages: 5438-5446

    DOI:10.1021/jp905895w

    Published: APR 1 2010

      Abstract:

        Evidence obtained by experiments in the vas phase and density   functional theory calculations indicates that differences in the   CO binding energy to the transition metal site and the overall   change in energy and spin multiplicity from reactants to   products, underlie the variation in relative reactivity observed   for the oxidation of CO by anionic transition metal oxide   clusters. Experimental reactivity Studies of MO(2)(-) and   M(2)O(3)(-) (M = Fe, Co, Ni, and Cu) reveal that anionic oxide   clusters with the same number of atoms and stoichiometry but   different elemental composition exhibit specific trends in   relative oxidation reactivity with CO. The anionic MO(2)(-) and   M(2)O(3)(-) clusters are found to be most reactive for M = Fe and   Cu and relatively less reactive for M = Co and Ni. Theoretical   electronic structure Studies within the density functional theory   framework indicate that the most reactive clusters either have   relatively large initial binding energies of CO to the cluster   which provide sufficient energy to overcome any subsequent   barriers to oxidation, or that the reaction preserves the same   overall spin multiplicity from reactants to products.

      Address (URL): http://pubs.acs.org/doi/full/10.1021/jp905895w