Boosting Electrocatalytic CO ₂ Reduction to Multi‐Carbon Products via Modulated Asymmetric Cu Sites

Abstract Electrocatalytic carbon dioxide reduction reaction (CO 2 RR) into high‐value products on Cu‐based catalysts holds promise for achieving carbon neutrality. However, the productivity toward multi‐carbon products in CO 2 RR is insufficient for practical applications owing to limited * CO dimerization process, especially under high current operation. Here, the Ag‐doped oxide‐derived Cu nanosheets (CuAg x% NSs) catalysts are reported via tailoring Ag in Cu NSs at an atomic‐level to form C 2+ products. The CuAg 0.123% NSs achieved a significant Faradaic efficiency of 77.5% and 71.3% toward multi‐carbon products at 300 and 500 mA cm −2 , respectively. Theoretical calculations and in situ characterizations reveal that the single‐atomic Ag‐doped Cu facet generates asymmetric CO‐adsorbed Cu sites, stabilizing * CO adsorption and further triggering C─C coupling for C 2+ products. This work emphasizes the significance of asymmetric sites of Cu‐based catalysts for fine regulation of the critical intermediate * CO to enhance *CO dimerization for C 2+ products.