The Role of Reducible Oxide–Metal Cluster Charge Transfer in Catalytic Processes: New Insights on the Catalytic Mechanism of CO Oxidation on Au/TiO from ab Initio Molecular Dynamics.

To probe metal particle/reducible oxide interactions density functional theory based ab initio molecular dynamics studies were performed on a prototypical metal cluster (Au) supported on reducible oxides (rutile TiO(110)) to implicitly account for finite temperature effects and the role of excess su...

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Publicado en:Journal of the American Chemical Society Vol. 135; no. 29; pp. 10673 - 10684
Autores principales: Yang-Gang Wang, Yeohoon Yoon, Glezakou, Vassiliki-Alexandra, Jun Li, Rousseau, Roger
Formato: Artículo
Publicado: American Chemical Society 7/24/2013
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Acceso en línea:Ver este registro en EBSCOhost
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        atl: The Role of Reducible Oxide–Metal Cluster Charge Transfer in Catalytic Processes: New Insights on the Catalytic Mechanism of CO Oxidation on Au/TiO from ab Initio Molecular Dynamics.
      aug:
        au:
          Yang-Gang Wang
          Yeohoon Yoon
          Glezakou, Vassiliki-Alexandra
          Jun Li
          Rousseau, Roger
        affil:
          Department of Chemistry, Tsinghua University, Beijing, 100084, China
          Institute for Interfacial Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
      su:
        Metal clusters
        Oxidation of carbon monoxide
        Molecular dynamics
        Density functional theory
        Charge transfer
        Catalytic activity
        Gold clusters
        Titanium dioxide films
      sug:
        subj:
          Metal clusters
          Oxidation of carbon monoxide
          Molecular dynamics
          Density functional theory
          Charge transfer
          Catalytic activity
          Gold clusters
          Titanium dioxide films
      ab: To probe metal particle/reducible oxide interactions density functional theory based ab initio molecular dynamics studies were performed on a prototypical metal cluster (Au) supported on reducible oxides (rutile TiO(110)) to implicitly account for finite temperature effects and the role of excess surface charge in the metal oxide. It is found that the charge state of the Au particle is negative in a reducing chemical environment whereas in the presence of oxidizing species coadsorbed to the oxide surface the cluster obtained a net positive charge. In the context of the well-known CO oxidation reaction, charge transfer facilitates the plasticization of Au, which allows for a strong adsorbate induced surface reconstruction upon addition of CO leading to the formation of mobile Au–CO species on the surface. The charging/discharging of the cluster during the catalytic cycle of CO oxidation enhances and controls the amount of O adsorbed at oxide/cluster interface and strongly influences the energetics of all redox steps in catalytic conversions. A detailed comparison of the current findings with previous studies is presented, and generalities about the role of surface-adsorbate charge transfer for metal cluster/reducible oxide interactions are discussed.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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