In‐Induced Electronic Structure Modulations of Bi─O Active Sites for Selective Carbon Dioxide Electroreduction to Liquid Fuel in Strong Acid

The formation of carbonate in neutral/alkaline solutions leads to carbonate crossover, severely reducing carbon dioxide (CO₂ ) single pass conversion efficiency (SPCE). Thus, CO₂ electrolysis is a prospective route to achieve high CO₂ utilization under acidic environment. Bimetallic Bi-based catalysts obtained utilizing metal doping strategies exhibit enhanced CO₂ -to-formic acid (HCOOH) selectivity in alkaline/neutral media. However, achieving high HCOOH selectivity remains challenging in acidic media. To this end, Indium (In) doped Bi2O2CO3 via hydrothermal method is prepared for in-situ electroreduction to In-Bi/BiOx nanosheets for acidic CO2 reduction reaction (CO2RR). In doping strategy regulates the electronic structure of Bi, promoting the fast derivatization of Bi2O2CO3 into Bi-O active sites to enhance CO2RR catalytic activity. The optimized Bi₂ O₂ CO₃ -derived catalyst achieves the maximum HCOOH faradaic efficiency (FE) of 96% at 200 mA cm^-2 . The SPCE for HCOOH production in acid is up to 36.6%, 2.2-fold higher than the best reported catalysts in alkaline environment. Furthermore, in situ Raman and X-ray photoelectron spectroscopy demonstrate that In-induced electronic structure modulation promotes a rapid structural evolution from nanobulks to Bi/BiO_x nanosheets with more active species under acidic CO₂ RR, which is a major factor in performance improvement.