Ji‐Long Sang, Qing Liu, Yi Zhang, Min Liu
Silver-based catalysts are among the most promising materials for the electrochemical CO2 reduction reaction (CO2RR), but they predominantly produce carbon monoxide (CO), limiting their utility in generating higher-value multi-carbon products. Here, we report a facile confined etching and epitaxial growth strategy to synthesize “corn-shaped” AgPd@Cu core–shell nanowires. This unique structure of the “corn-shaped” AgPd@Cu nanowires is conducive to the efficient generation and maintenance of high local CO concentration, and provides the optimal active sites for the dimerization reaction of CO. It enables a critical transition from C1 to C2 product formation, achieving a Faradaic efficiency of 38.80% for ethylene (C2H4) at −1.50 V vs. RHE with outstanding catalytic stability. The architecture (corn-shaped) is expected to enhance catalytic performance due to the increased surface area and interface synergy. The interfacial synergy between the AgPd core and Cu shell selectively suppresses the hydrogen evolution reaction and promotes C–C coupling, facilitating enhanced CO2-to-C2 conversion. This study not only addresses the challenge of C–C bond formation in CO2RR but also presents a generalizable strategy for constructing robust, multi-metallic nanocatalysts capable of operating under strongly reducing conditions.