Highly Efficient CO2 Electroreduction to Methanol through Atomically Dispersed Sn Coupled with Defective CuO Catalysts

Abstract Using renewable electricity to drive CO 2 electroreduction is an attractive way to achieve carbon‐neutral energy cycle and produce value‐added chemicals and fuels. As an important platform molecule and clean fuel, methanol requires 6‐electron transfer in the process of CO 2 reduction. Currently, CO 2 electroreduction to methanol suffers from poor efficiency and low selectivity. Herein, we report the first work to design atomically dispersed Sn site anchored on defective CuO catalysts for CO 2 electroreduction to methanol. It exhibits high methanol Faradaic efficiency (FE) of 88.6 % with a current density of 67.0 mA cm −2 and remarkable stability in a H‐cell, which is the highest FE(methanol) with such high current density compared with the results reported to date. The atomic Sn site, adjacent oxygen vacancy and CuO support cooperate very well, leading to higher double‐layer capacitance, larger CO 2 adsorption capacity and lower interfacial charge transfer resistance. Operando experiments and density functional theory calculations demonstrate that the catalyst is beneficial for CO 2 activation via decreasing the energy barrier of *COOH dissociation to form *CO. The obtained key intermediate *CO is then bound to the Cu species for further reduction, leading to high selectivity toward methanol.