Selective CO₂ Electroreduction to Formate on Polypyrrole-Modified Oxygen Vacancy-Rich Bi₂ O₃ Nanosheet Precatalysts...

Challenges remain in the development of highly efficient catalysts for selective electrochemical transformation of carbon dioxide (CO₂ ) to high-valued hydrocarbons. In this study, oxygen vacancy-rich Bi₂ O₃ nanosheets coated with polypyrrole (Bi₂ O₃ @PPy NSs) are designed and synthesized, as precatalysts for selective electrocatalytic CO₂ reduction to formate. Systematic material characterization demonstrated that Bi₂ O₃ @PPy precatalyst can evolve intoBi₂ O₂ CO₃ @PPy nanosheets with rich oxygen vacancies (Bi₂ O₂ CO₃ @PPy NSs) via electrolyte-mediated conversion and function as the real active catalyst for CO₂ reduction reaction electrocatalysis. Coating catalyst with a PPy shell can modulate the interfacial microenvironment of active sites, which work in coordination with rich oxygen vacancies in Bi₂ O₂ CO₃ and efficiently mediate directional selective CO₂ reduction toward formate formation. With the fine-tuning of interfacial microenvironment, the optimized Bi₂ O₃ @PPy-2 NSs derived Bi₂ O₂ CO₃ @PPy-2 NSs exhibit a maximum Faradaic efficiency of 95.8% at -0.8 V (versus. reversible hydrogen electrode) for formate production. This work might shed some light on designing advanced catalysts toward selective electrocatalytic CO₂ reduction through local microenvironment engineering.