Tuning Multi‐Active Sites in Cu Catalyst via Ag/Ni Doping for Enhanced CO 2 Electroreduction to C 2+ Products

Abstract Electrochemical CO 2 reduction (ECR) to C 2+ products is a promising sustainable carbon conversion pathway, yet simultaneously achieving high Faradaic efficiency (FE) and current density remains a challenge. Herein, we found that creating Cu‐Ag‐Ni multi‐metal sites could effectively modulate the adsorption energies of *H and *CO on the catalyst surface, thereby achieving highly efficient ECR to synthesize C 2+ products. In situ measurements coupling theoretical calculations indicated that by systematically altering the spatial arrangement and distribution of active sites in Cu‐Ag‐Ni catalysts, the electronic structure and the local *CO coverage on the Cu surface could be tuned, consequently steering the ECR to C 2+ pathway. In particular, Cu‐Ag‐Ni catalyst with dispersed multi‐sites (Cu x AgNi DNPs) could more effectively reduce the energy barrier for C─C coupling than Cu‐Ag‐Ni catalyst with phase‐separated multi‐sites (Cu x AgNi PNPs). As a result, the Cu 40 AgNi DNPs catalyst with dispersed multi‐sites yielded C 2+ products with a FE of 93.2% and a current density up to 818.1 mA cm −2 at −1.38 V versus reversible hydrogen electrode (vs. RHE), which are higher than most reported up to date for C 2+ production. This work provides a methodology for designing robust multi‐metallic ECR catalysts with tailored multi‐active site configurations.