Promoting CO₂ Electroreduction Kinetics on Atomically Dispersed Monovalent Zn^I Sites by Rationally Engineering...

Electrocatalytic reduction of CO₂ (CO₂ RR) to value-added chemicals is of great significance for CO₂ utilization, however the CO₂ RR process involving multi-electron and proton transfer is greatly limited by poor selectivity and low yield. Herein, We have developed an atomically dispersed monovalent zinc catalyst anchored on nitrogenated carbon nanosheets (Zn/NC NSs). Benefiting from the unique coordination environment and atomic dispersion, the Zn/NC NSs exhibit a superior CO₂ RR performance, featuring a high current density up to 50 mA cm^-2 with an outstanding CO Faradaic efficiency of ≈95 %. The center Zn^I atom coordinated with three N atoms and one N atom that bridges over two adjacent graphitic edges (Zn-N₃₊₁ ) is identified as the catalytically active site. Experimental results reveal that the twisted Zn-N₃₊₁ structure accelerates CO₂ activation and protonation in the rate-determining step of *CO₂ to *COOH, while theoretical calculations elucidate that atomically dispersed Zn-N₃₊₁ moieties decrease the potential barriers for intermediate COOH* formation, promoting the proton-coupled CO₂ RR kinetics and boosting the overall catalytic performance.