Achieving Tunable Selectivity and Activity of CO₂ Electroreduction to CO via Bimetallic Silver-Copper Electronic...

Limited comprehension of the reaction mechanism has hindered the development of catalysts for CO₂ reduction reactions (CO₂ RR). Here, the bimetallic AgCu nanocatalyst platform is employed to understand the effect of the electronic structure of catalysts on the selectivity and activity for CO₂ electroreduction to CO. The atomic arrangement and electronic state structure vary with the atomic ratio of Ag and Cu, enabling tunable d-band centers to optimize the binding strength of key intermediates. Density functional theory calculations confirm that the variation of Cu content greatly affects the free energy of *COOH, *CO (intermediate of CO), and *H (intermediates of H₂ ), which leads to the change of the rate-determining step. Specifically, Ag₉₆ Cu₄ reduces the free energy of the formation of *COOH while maintaining a relatively high theoretical overpotential for hydrogen evolution reaction(HER), thus achieving the best CO selectivity. While Ag₇₀ Cu₃₀ shows relatively low formation energy of both *COOH and *H, the compromised thermodynamic barrier and product selectivity allows Ag₇₀ Cu₃₀ the best CO partial current density. This study realizes the regulation of the selectivity and activity of electrocatalytic CO₂ to CO, which provides a promising way to improve the intrinsic performance of CO₂ RR on bimetallic AgCu.