Anion Exchange Facilitates the In Situ Construction of Bi/Bi-O Interfaces for Enhanced Electrochemical CO₂-to-Formate Conversion Over a Wide Potential Window

Electrochemical reduction of CO₂ (CO₂RR) into value-added products is a promising strategy to reduce energy consumption and solve environmental issues. Formic acid/formate is one of the high-value, easy-to-collect, and economically viable products. Herein, the reconstructed Bi₂O₂CO₃ nanosheets (BOC_R NSs) are synthesized by an in situ electrochemical anion exchange strategy from Bi₂O₂SO₄ as a pre-catalyst. The BOC_R NSs achieve a high formate Faradaic efficiency (FE_formate) of 95.7% at −1.1 V versus reversible hydrogen electrode (vs. RHE), and maintain FE_formate above 90% in a wide potential range from −0.8 to −1.5 V in H-cell. The in situ spectroscopic studies reveal that the obtained BOC_R NSs undergo the anion exchange from Bi₂O₂SO₄ to Bi₂O₂CO₃ and further promote the self-reduction to metallic Bi to construct Bi/Bi-O active site to facilitate the formation of OCHO^* intermediate. This result demonstrates anion exchange strategy can be used to rational design high performance of the catalysts toward CO₂RR.