Catalytic Oxidation of Benzyl Alcohol to Benzaldehyde on Au8 and Au6Pd2 Clusters: A DFT Study on the Reaction Mechanism

Density functional theory calculations were performed to investigate the reaction mechanism of aerobic oxidation benzyl alcohol benzaldehyde catalyzed by Au and Au–Pd clusters. Two consecutive mechanisms examined with Au8 Au6Pd2 clusters: (1) dissociated O atoms on metal clusters generating H2O; (2) adsorbed oxygen molecules H2O2. The show that energetically prefers proceed in former mechanism, which agrees experimental observation. We demonstrate role centers around activation molecular peroxide-like species, are capable H–abstraction alcohol. roles Pd cluster are: increasing electron distribution neighboring atoms, facilitates O2; stabilizing adsorption complex transition states interaction between positively charged π-bond alcohol, both origin lower energy barriers than those Au8.