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 FE_C2+ 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.