Bimetallic In 2 O 3 / Bi 2 O 3 catalysts enable highly selective CO 2 electroreduction to formate within ultra‐broad potential windows

CO 2 electrochemical reduction reaction (CO 2 RR) to formate is a hopeful pathway for reducing CO 2 and producing high‐value chemicals, which needs highly selective catalysts with ultra‐broad potential windows to meet the industrial demands. Herein, the nanorod‐like bimetallic In 2 O 3 /Bi 2 O 3 catalysts were successfully synthesized by pyrolysis of bimetallic InBi‐MOF precursors. The abundant oxygen vacancies generated from the lattice mismatch of Bi 2 O 3 and In 2 O 3 reduced the activation energy of CO 2 to and improved the selectivity of to formate simultaneously. Meanwhile, the carbon skeleton derived from the pyrolysis of organic framework of InBi‐MOF provided a conductive network to accelerate the electrons transmission. The catalyst exhibited an ultra‐broad applied potential window of 1200 mV (from −0.4 to −1.6 V vs RHE), relativistic high Faradaic efficiency of formate (99.92%) and satisfactory stability after 30 h. The in situ FT‐IR experiment and DFT calculation verified that the abundant oxygen vacancies on the surface of catalysts can easily absorb CO 2 molecules, and oxygen vacancy path is dominant pathway. This work provides a convenient method to construct high‐performance bimetallic catalysts for the industrial application of CO 2 RR.