Ab initio study of the adsorption of SO2 on single-atom Cu-decorated ZnO(0001) surface

Context The World Health Organization has cataloged sulfur dioxide (SO 2 ) as harmful for the human health and the environment. It also contributes to generate acid rain, which affects the ecosystems. To reduce its negative effects, new strategies to control the emissions are required. New and engineered materials are investigated to detect, capture, and eradicate toxic gases from the environment. Zinc oxide is considered a promising candidate. Here, we investigate the Cu-decorated ZnO(0001) surfaces as a single-atom catalyst (SAC) to reduce SO 2 by first-principles calculations. We propose a two-step reduction mechanism. First, one of the S–O bonds is broken on the pristine surface, with a calculated activation energy of 14.76 kcal/mol, 1.84 kcal/mol larger than the one obtained in the Cu SAC. In the second step, the SO reduction is viable only for Cu SAC, with calculated activation energy of 29.28 kcal/mol. Our results point that Cu SAC improves the SO 2 reduction, pointing it as a potentially efficient device to eradicate such harmful pollutant from the environment. Methods The calculations were performed using the density functional theory, as implemented in quantum ESPRESSO package. The exchange–correlation energy was calculated within the generalized gradient approximation with the Perdew–Burke–Ernzerhof parameterization. Van der Waals dispersion-corrected interactions were considered. Spin-polarization was considered for studying dangling bonds in transition states. The minimum energy pathways were calculated by using the climbing image nudged elastic band.