Synergistic Effect of Nickel and Calcium Dual-Atomic Sites to Facilitate Electrochemical CO2 Reduction to Methanol: Combining High Activity and Selectivity

Atomically dispersed transition metal sites embedded into nitrogen-doped graphene provide promising potential for the electrochemical CO2 reduction to CO, but the catalytic efficiency for further hydrogenation to methanol is seriously restricted. Herein, combining the advantage of single transition metal, alkaline-earth metal, and multiple active sites, we designed nickel and calcium dual-atomic site catalysts (Ni-Ca DACs) supported on N-doped graphene to enable CO2 hydrogenation. First-principles calculations reveal that the electron-rich Ni atom serves as the carbon adsorption site, and the adjacent Ca atom with electron-deficient properties acts as the oxygen adsorption site, which largely stabilizes many CHxOy species through the O-Ca bond, especially the *OCHO, thus facilitating CO2 reduction. More importantly, a synergistic adsorption process on Ni-Ca sites promote the formation of *CHO species that is considered as the key intermediate for generation of multi-electron products. Different from the single Ni or Ca catalysts that produce mainly CO or HCOOH, the Ni-Ca DACs can selectively catalyze CO2 reduction to CH3OH, with a low limiting potential of -0.52 V, while suppressing the hydrogen evolution reaction. The outstanding catalytic activity originates from the tuned polarized charge and d-band center of active sites by synergistic interaction of adjacent Ni and Ca atoms.