Enhanced performance of oxygen vacancies on CO2 adsorption and activation over different phases of ZrO2

The effect of oxygen vacancies on the adsorption and activation of CO₂ on the surface of different phases of ZrO₂ is investigated by density functional theory (DFT) calculations. The calculations show that the oxygen vacancies contribute greatly to both the adsorption and activation of CO₂. The adsorption energy of CO₂ on the c-ZrO₂, t-ZrO₂ and, m-ZrO₂ surfaces is enhanced to 5, 4, and 3 folds with the help of oxygen vacancies, respectively. Moreover, the energy barrier of CO₂ dissociation on the defective surfaces of c-ZrO₂, t-ZrO₂, and m-ZrO₂ is reduced to 1/2, 1/4, and 1/5 of the perfect surface with the assistance of oxygen vacancies. Furthermore, the activation of CO₂ on the ZrO₂ surface where oxygen vacancies are present, and changes from an endothermic reaction to an exothermic reaction. This finding demonstrates that the presence of oxygen vacancies promotes the activation of CO₂ both kinetically and thermodynamically. These results could provide guidance for the high-efficient utilization of CO₂ at an atomic scale.