Theoretical calculation guided design of single atom-alloyed bismuth catalysts for ampere-level CO₂ electrolysis to formate

Electrochemically reducing CO₂ (CO₂RR) to value-added fuels is a promising strategy to achieve carbon neutralization. Nowadays Bi-based catalysts suffer from limited activity, selectivity, and stability under harsh condition. Herein, under the guidance of density functional theory calculations, Zn single-atom alloyed metallic Bi (SAA-Zn₁Bi) was screened out as the remarkable CO₂RR catalyst for formate production. As expected, SAA-Zn₁Bi, synthesized by a two-step in-situ electrochemical reduction strategy, delivered an industrial-compatible current density of − 1323 mA cm⁻² and exhibited a record formate formation rate of 24.5 mmol·h⁻¹·cm⁻² at − 0.86 V versus the reversible hydrogen electrode. Importantly, the durability reaches 250 h at − 400 mA cm⁻² was realized. The in-situ experimental explorations revealed that SAA-Zn₁Bi benefited from its moderately adsorbed *OCHO intermediate, matched well with the precast of the theoretical calculations. This work is highly instructive for the design of SAAs electrocatalysts and provides a new avenue for the fabrication of Bi-based SAAs electrocatalysts.