Synergistic Acceleration of CO ₂ Electroreduction Kinetics by Oxygen Vacancy and Heterogeneous Interface for Efficient HCOOH Production

Abstract Constructing highly efficient bismuth (Bi)‐based catalysts to accelerate the sluggish kinetic process of CO ₂ electroreduction to HCOOH is crucial for promoting its practical application but also highly challenging. Herein, the bismuth cerium oxide catalyst integrated with dual active centers of oxygen vacancy and the heterogeneous interface is fabricated to facilitate the reduction process and enhance the CO ₂ electroreduction performance. It is revealed that the introduction of dual active centers endows the catalyst with a remarkably enhanced CO ₂ adsorption capacity and facilitates the transfer of more electrons to ^* CO ₂ . Furthermore, it even steers the reaction pathway favorably toward HCOOH production. The optimization of CO ₂ adsorption, activation, and reaction energy barriers expedited the process of CO ₂ electroreduction to HCOOH. As expected, this catalyst exhibits enhanced catalytic performance with a Faradaic efficiency of 97% for HCOOH even at the current density of 300 mA cm ⁻² . This work highlights the significant synergistic advantages of oxygen vacancies and heterogeneous interfaces in optimizing molecular adsorption, activation, and reaction energy barriers to accelerate the kinetic process.