Theoretical studies on the catalytic activity of Ag surface for the oxidation of olefins

Hiroshi Nakatsuji, Zhen Ming Hu, Hiromi Nakai

    Research output: Contribution to journalArticle

    30 Citations (Scopus)

    Abstract

    Systematic theoretical studies for the mechanisms of the epoxidation and complete oxidation of ethylene and propylene over silver surface as well as the reactivity and the stability of oxygen species on Cu, Ag, and Au surfaces have been presented. The dipped adcluster model (DAM) combined with the ab initio Hartree-Fock (HF), second-order Møller-Plesset (MP2), and SAC/SAC-CI (symmetry-adapted cluster/configuration interaction) methods are used. These studies clarify the origin of silver as a unique effective catalyst for the epoxidation of ethylene and the different mechanisms for the oxidation of olefins over silver surface. For the epoxidation of ethylene, the superoxide O2 -, which is molecularly adsorbed in bent end-on geometry on the silver surface, is the active species. The origin of the unique catalytic activity of silver for the epoxidation of ethylene is due to its ability to adsorb oxygen as the superoxide species. Such an adsorbed species cannot be stable or exist on Cu and Au surfaces. For the oxidation of propylene, both reaction mechanisms initiated by the activation of olefinic carbon and by the activation of the allyl hydrogen exist. The activation of the allyl hydrogen is the origin of the complete oxidation of some olefins over silver surface. The present results not only let us have a better understanding of the reaction mechanisms of olefins over silver surface but also supply a basic idea for the new catalyst design of the epoxidation reaction.

    Original languageEnglish
    Pages (from-to)839-855
    Number of pages17
    JournalInternational Journal of Quantum Chemistry
    Volume65
    Issue number5
    Publication statusPublished - 1997

    Fingerprint

    Alkenes
    Silver
    alkenes
    catalytic activity
    epoxidation
    Epoxidation
    Catalyst activity
    silver
    Oxidation
    oxidation
    ethylene
    inorganic peroxides
    Chemical activation
    activation
    propylene
    Superoxides
    Hydrogen
    Oxygen
    catalysts
    Catalysts

    ASJC Scopus subject areas

    • Physical and Theoretical Chemistry

    Cite this

    Theoretical studies on the catalytic activity of Ag surface for the oxidation of olefins. / Nakatsuji, Hiroshi; Hu, Zhen Ming; Nakai, Hiromi.

    In: International Journal of Quantum Chemistry, Vol. 65, No. 5, 1997, p. 839-855.

    Research output: Contribution to journalArticle

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