Water Adsorption and Dissociation on Ceria-Supported Single-Atom Catalysts: A First-Principles DFT plus U Investigation

Single-atom catalysts have attracted wide attention owing to their extremely high atom efficiency and activities. In this paper, we applied density functional theory with the inclusion of the on-site Coulomb interaction (DFT+U) to investigate water adsorption and dissociation on clean CeO2(111) surfaces and single transition metal atoms (STMAs) adsorbed on the CeO2(111) surface. It is found that the most stable water configuration is molecular adsorption on the clean CeO2(111) surface and dissociative adsorption on STMA/CeO2(111) surfaces, respectively. In addition, our results indicate that the more the electrons that transfer from STMA to the ceria substrate, the stronger the binding energies between the STMA and ceria surfaces. A linear relationship is identified between the water dissociation barriers and the d band centers of STMA, known as the generalized BrOnsted-Evans-Polanyi principle. By combining the oxygen spillovers, single-atom dispersion stabilities, and water dissociation barriers, Zn, Cr, and V are identified as potential candidates for the future design of ceria-supported single-atom catalysts for reactions in which the dissociation of water plays an important role, such as the water-gas shift reaction.