Electrothermally Catalytic CO ₂ Selective Hydrogenation to Methanol on Electric Field‐Responsive Cu/in ₂ O ₃ Catalyst

Abstract The Cu and In 2 O 3 ‐based catalysts are broadly utilized in CO 2 hydrogenation to methanol, however, they often suffer from the limitations of catalytic activity, selectivity, and stability. Herein, a kind of functional Cu/In 2 O 3 catalyst having unique physicochemical properties under an imposed electric field is developed for efficient and selective CO 2 hydrogenation to methanol. Distinct from the conventional thermally catalytic process, the intensification of an external electric field will facilitate the reduction Cu + to Cu 0 species and formation of oxygen vacancy in In 2 O 3 and modulate CO 2 adsorption and desorption behavior, which consequently promote the effective activation of CO 2 and H 2 to selectively produce methanol other than CO. As a result, the space‐time yield of methanol can reach up to 130.4 mg g Cat h −1 with selectivity of 97.9%, which remarkably surpasses the reported system even using noble metal at comparable hydrogenation condition. Structure‐activity analysis indicates the content of Cu 0 and oxygen vacancy in catalyst show linear relationships with CO 2 transformative rate and methanol selectivity, respectively. In situ mechanism investigation reveals that the CO 2 ‐to‐methanol hydrogenation follows the formate pathway under an electric field which accelerates the generation of HCOO * and CH 3 O * . This work will provide a new strategy for efficient CO 2 selective hydrogenation to methanol.