Atomically Dispersed Ga Synergy Lewis Acid‐Base Pairs in F‐doped Mesoporous Cu2O for Efficient Eletroreduction of CO2 to C2+ Products

Abstract Electroreduction of CO2 into high‐value chemicals and fuels driven is an effective way to alleviate the environmental crisis, but it suffers from poor activity and low selectivity of the catalyst. Single‐atom catalysts have excellent selectivity and the highest atomic efficiency, and are widely used in the 2‐electron transfer to produce CO. However, electroreduction of CO2 to C2+ products involves complex processes such as multi‐electron reaction and competitive adsorption, so single‐atom catalysis is often powerless. Herein, a single‐atom Ga‐anchored F‐doped Cu2O catalyst with dual active sites is reported. The Lewis acid‐base pairs and Ga single atom sites promote the adsorption/activation of CO2 and the dissociation of water molecules, respectively, enhance the coverage of *CO and *H, and their synergy optimizes the reaction path. At a high current density of 600 mA cm−2, the FEC2+ reached 72.8 ± 3.2% with remarkable stability. Experiments and theory calculations demonstrate that the dual sites increase the coverage of *CO and *H, and the key intermediate *CO is transformed into *CHO through protonation reaction, which changes the reaction path from the C─C coupling (*OCCO) to the protonation followed by C─C coupling (*OCCHO) with low energy barrier, greatly improving the selectivity for C2+ products.