Tuning Electronic Effects in P‐Block Metal‐C ₆₀ Catalysts for Highly Selective CO ₂ Reduction to Formate

ABSTRACT Electrochemical CO ₂ reduction (CO ₂ R) to formate offers a promising pathway toward sustainable chemical production. Although P‐block metals display excellent selectivity, a universal approach for electronically tuning their active sites to simultaneously enhance activity and selectivity has remained challenging. In this work, we employ C ₆₀ nanosheets as electron‐buffering supports to modulate interfacial charge, and hence to improve the performance of P‐block metals in CO ₂ R. Compared with pure indium (Pure In) catalyst, the C ₆₀ nanosheets supported In nanoclusters catalyst (In−C ₆₀ ) featuring high oxidation state achieves formate‐dominated products across wide current densities, with high faradaic efficiency for formate reaching about 93% at 900 mA cm ⁻² under alkaline conditions and 97% at 700 mA cm ⁻² in acid, as well as higher stability exceeding 210 h in alkaline media. Operando infrared spectroscopy reveals that In−C ₆₀ promotes ^* OCHO formation, and fixed‐potential density functional theory (DFT) calculations indicate that C ₆₀ tunes the In─O antibonding states near the Fermi level, weakening intermediate binding and facilitating the following protonation to formate. The strategy extends to other P‐block metals (Bi, Sn, Pb), with the same electronic‐tuning effect. This work introduces a generalizable strategy for P‐block metal electrocatalysts and a practical route toward efficient, sustainable chemical production.