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.