Defective Bimetallic Selenides for Selective CO₂ Electroreduction to CO

Abstract CO₂ electroreduction (CO₂RR) to CO is promising for the carbon cycle but still remains challenging. Au is regarded as the most selective catalyst for CO₂RR, but its high cost significantly hinders its industrial application. Herein, the bimetallic CuInSe₂ is found to exhibit an Au‐like catalytic feature: i) the interaction of Cu and In orbitals induces a moderate adsorption strength of CO₂RR intermediates and favors the reaction pathway; and ii) the hydrogen evolution is energetically unfavorable on CuInSe₂, as a surface reconstruction along with high energy change will occur after hydrogen adsorption. Furthermore, the Se vacancy is found to induce an electron redistribution, slightly tune the band structure, and optimize the CO₂RR route of bimetallic selenide. Consequently, the Se‐defective CuInSe₂ (V‐CuInSe₂) achieves a highly selective CO production ability that is comparable to noble metals in aqueous electrolyte, and the V‐CuInSe₂ cathode shows a satisfactory performance in an aqueous Zn–CO₂ cell. This work demonstrates that designing cost‐effective catalysts with noble‐metal‐like properties is an ideal strategy for developing efficient electrocatalysts. Moreover, the class of transition bimetallic selenides has shown promising prospects as active and cost‐effective electrocatalysts owing to their unique structural, electronic, and catalytic properties.