The Role of Reducible Oxide–Metal Cluster Charge Transfer in Catalytic Processes: New Insights on the Catalytic Mechanism of CO Oxidation on Au/TiO2 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 (Au20) supported on reducible oxides (rutile TiO2(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 Au20, 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 O2 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.