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.