Selective CO Electroreduction to Multicarbon Oxygenates over Atomically Dispersed Cu‐Ag Sites in Alkaline Membrane Electrode Assembly Electrolyzer

Electrochemical carbon monoxide reduction reaction (CORR) to produce multicarbon (C2+) oxygenates using renewable electricity is a promising carbon utilization pathway. However, the performance of this process suffers from low C2+ oxygenates selectivity and insufficient current density. Here, we employed a Cu‐Ag bimetallic strategy to enhance the selectivity of C2+ oxygenates from CORR in alkaline membrane electrode assembly electrolyzer at ampere‐level current densities. The Cu‐Ag catalysts prepared by magnetron sputtering feature atomically dispersed Cu‐Ag sites on the catalyst surface, which are key to promote the formation of C2+ oxygenates. Increasing Ag content favors C2+ oxygenates formation while inhibiting ethylene production. The optimized Cu2Ag catalyst achieved Faradaic efficiency of 71.4% for C2+ oxygenates at 2.5 A cm‐2. In situ spectroscopy and density functional theory calculations revealed that atomically dispersed Cu‐Ag sites on the catalyst surface promote the dissociation of *COCOH to *CCO, thus favoring C2+ oxygenates formation.