Adsorption and dissociation of O2 on the Cu2O(1 1 1) surface: Thermochemistry, reaction barrier

The adsorption and dissociation of O2 on the perfect and oxygen-deficient Cu2O(1 1 1) surface have been systematically studied using periodic density functional calculations. Different kinds of possible modes of atomic O and molecular O2 adsorbed on the Cu2O(1 1 1) surface are identified: atomic O is found to prefer threefold 3Cu site on the perfect surface and Ovacancy site on the deficient surface, respectively. CuCUS is the most advantageous site with molecularly adsorbed O2 lying flatly over singly coordinate CuCUS-CuCSA bridge on the perfect surface. O2 adsorbed dissociatively on the deficient surface, which is the main dissociation pathway of O2, and a small quantity of molecularly adsorbed O2 has been obtained. Further, possible dissociation pathways of molecularly adsorbed O2 on the Cu2O(1 1 1) surface are explored, the reaction energies and relevant barriers show that a small quantity of molecularly adsorbed O2 dissociation into two O atoms on the deficient surface is favorable both thermodynamically and kinetically in comparison with the dissociation of O2 on the perfect surface. The calculated results suggest that the presence of oxygen vacancy exhibits a strong chemical reactivity towards the dissociation of O2 and can obviously improve the catalytic activity of Cu2O, which is in agreement with the experimental observation.

Research highlights▶ Dissociative adsorption is the main dissociation path of O2 on the deficient surface. ▶ The oxygen species adsorbed show the characteristic of the peroxo form (O22−). ▶ The oxygen vacancy exhibits strong catalytic activity for O2 dissociation. ▶ CuCUS is the advantageous site for O2 adsorbed molecularly on the perfect surface.