Defect‐Rich Heterostructured Bi‐Based Catalysts for Efficient CO2 Reduction Reaction to Formate in Wide Operable Windows

Electrocatalytic reduction of CO 2 to formate is believed to be one of the most promising technologies for producing clean fuels and valuable chemicals and for tackling the global warming problem. Herein, a novel synthesis strategy is presented for Bi‐based catalyst in CO 2 reduction reaction (CO 2 RR). With the addition of acetic acid into the mother solution, heterostructured Bi/Bi 2 O 3 nanoplates with abundant O vacancies (Bi/Bi 2 O 3 –O v ) and tailored coordination environments of the Bi ions are successfully synthesized, which exhibit excellent catalytic activity for CO 2 RR and high selectivity for formate generation with wide operable windows of pH (neutral to alkaline) and potential. In particular, the faradic efficiency (HCOOH) reaches ≥90% in a wide potential range of −0.7–−1.35 V versus reversible hydrogen electrode in neutral media, which dwarf most of the state‐of‐the‐art Bi‐based catalysts for CO 2 RR reported to date. Combined experimental and theoretical results show that the abundant O vacancies create frustrated Lewis pairs at the heterointerfaces with favorable adsorption characteristics, thereby facilitating the CO 2 RR process. This work opens up a new approach to promoting the catalytic activity and selectivity of Bi‐based materials for CO 2 RR by combining coordination and heterointerface engineering.