In Situ Bismuth Nanosheet Assembly for Highly Selective Electrocatalytic CO₂ Reduction to Formate

The reduction of carbon dioxide (CO₂ ) into value-added fuels using an electrochemical method has been regarded as a compelling sustainable energy conversion technology. However, high-performance electrocatalysts for CO₂ reduction reaction (CO₂ RR) with high formate selectivity and good stability need to be improved. Earth-abundant Bi has been demonstrated to be active for CO₂ RR to formate. Herein, we fabricated an extremely active and selective bismuth nanosheet (Bi-NSs) assembly via an in situ electrochemical transformation of (BiO)₂ CO₃ nanostructures. The as-prepared material exhibits high activity and selectivity for CO₂ RR to formate, with nearly 94% faradaic efficiency at -1.03 V (versus reversible hydrogen electrode (vs. RHE)) and stable selectivity (>90%) in a large potential window ranging from -0.83 to -1.18 V (vs. RHE) and excellent durability during 12 h continuous electrolysis. In addition, the Bi-NSs based CO₂ RR/methanol oxidation reaction (CO₂ RR/MOR) electrolytic system for overall CO₂ splitting was constructed, evidencing the feasibility of its practical implementation.