Adsorption and dissociation of Cl2 on CuO(111) surface with first-principles study

Abstract

The first principle calculation based on density functional theory (DFT) was used to discuss the adsorption and dissociation behaviors of Cl2 on the perfect and oxygen-deficient surfaces of CuO(111) in this paper. The adsorption behavior and reaction mechanism of Cl2 directly adsorbed on two CuO(111) surfaces were analyzed by calculating the adsorption structure, energy of adsorption, charge density difference, the electron localization function and density of states (DOS) of the system. The calculations suggest that the most advantageous site for Cl2 adsorption on the perfect CuO(111) surface is the bridge site between two Cusub atoms. However, on the oxygen-deficient CuO(111) surface, two Cl atoms dissociated from the Cl2 molecule and bound to the Cu site after optimization. The calculations indicate that the existence of oxygen vacancy is highly chemically reactive when it comes to the dissociation of Cl2, which can increase the activity of CuO significantly. Our calculations of the adsorption and dissociation of Cl2 on the CuO(111) surface can offer some microscopic information for the side products of CuO and Cl2 produced by the thermolysis of copper oxychloride and the effect of side reaction on yield.