Interfacial P-Band Modulation in Bismuth for Electrocatalytic CO₂ Reduction Over Wide pH Ranges

Abstract

Heteroatom modification effectively tailors the electronic structure of the p-block metal for CO₂ reduction reaction, but the p-orbital hybridization of sulfur-induced in the electroreduction process remains unclear. Here, an in-situ electrochemical modification approach is developed to tailor bismuth catalysts coordinated with sulfur atoms. The pronounced interaction between bismuth and sulfur p orbital optimizes the electronic states for efficient CO₂ electroreduction, achieving high Faradaic efficiency of 95.5% for formate and near 100% selectivity for C₁ products, while maintaining 93% formate Faradaic efficiency under pH-universal electrolytes. In-situ characterization and theoretical calculations reveal a descriptor-based design principle, wherein tuning the sulfur atom configuration modulates bismuth p-orbital delocalization with an optimized p-band center, thereby reducing energy barrier for formate generation. Based on the fundamental insights, a solar-driven CO₂-H₂O electrolyzer was constructed with a FE_formate of 93.7% and an energy conversion efficiency of 13.9%. This work establishes an electronic structure design strategy based on p-orbital delocalization modulation, offering theoretical insights and practical guidance for developing advanced main-group metal electrocatalysts.

Keywords

electrocatalytic CO₂ reduction / interface modification / p-orbital delocalization

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