ZnO supported on Cu2O{1 0 0} enhances charge transfer in dimethyldichlorosilane synthesis

Abstract In this work, three types of ZnO/Cu 2 O heterostructures were synthesized by depositing ZnO nanoparticles on the supports of Cu 2 O cubes, Cu 2 O octahedrons and Cu 2 O dodecahedrons with different exposed facets. These catalysts were used for the Rochow reaction, which is an important industrial process for the synthesis of organosilicon polymers. It was demonstrated that Cu 2 O cubes-supported ZnO catalyst is the most active toward dimethyldichlorosilane formation, while Cu 2 O dodecahedrons-supported ZnO catalyst is the least active. Both experimental results and density functional theory calculations show that, in the three cases, the charge transfer efficiency between the ZnO nanoparticle and the Cu 2 O{1 0 0} plane is the highest, which enhances the dissociative adsorption of methylchloride at Cu 2 O{1 0 0}, the subsequent reduction of Cu + into Cu 0 and the final formation of the Cu 3 Si active phases. This work reveals essential information about how the Rochow reaction proceeds on the ZnO/Cu 2 O catalyst and demonstrates a practical strategy to rationally design highly efficient catalytic system in heterogeneous catalysis.