Oxophilicity-Controlled CO 2 Electroreduction to C 2+ Alcohols over Lewis Acid Metal-Doped Cu δ+ Catalysts.

Cu-based electrocatalysts have great potential for facilitating CO 2 reduction to produce energy-intensive fuels and chemicals. However, it remains challenging to obtain high product selectivity due to the inevitable strong competition among various pathways. Here, we propose a strategy to regulate the adsorption of oxygen-associated active species on Cu by introducing an oxophilic metal, which can effectively improve the selectivity of C 2+ alcohols. Theoretical calculations manifested that doping of Lewis acid metal Al into Cu can affect the C-O bond and Cu-C bond breaking toward the selectively determining intermediate (shared by ethanol and ethylene), thus prioritizing the ethanol pathway. Experimentally, the Al-doped Cu catalyst exhibited an outstanding C 2+ Faradaic efficiency (FE) of 84.5% with remarkable stability. In particular, the C 2+ alcohol FE could reach 55.2% with a partial current density of 354.2 mA cm -2 and a formation rate of 1066.8 μmol cm -2 h -1 . A detailed experimental study revealed that Al doping improved the adsorption strength of active oxygen species on the Cu surface and stabilized the key intermediate *OC 2 H 5 , leading to high selectivity toward ethanol. Further investigation showed that this strategy could also be extended to other Lewis acid metals.