Synergistic effect of nickel and calcium dual-atomic sites to facilitate electrochemical CO 2 reduction to methanol: Combining high activity and selectivity

Atomically dispersed transition metal sites embedded into nitrogen-doped graphene provide promising potential for the electrochemical CO 2 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 CO 2 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 CH x O y species through the O-Ca bond, especially the *OCHO, thus facilitating CO 2 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 CO 2 reduction to CH 3 OH, 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.