Transformation of Bi4Cl2S5 into sub-10 nm Bi2O2CO3 nanowires for electrochemical reduction of CO2

Abstract

The development of highly efficient catalysts for the selective electrochemical reduction reaction of CO2 (eCO2RR) to high-valued formate remains a challenge in achieving carbon neutrality and renewable energy conversion. In this study, ultrathin Bi4Cl2S5 nanowires, synthesized using different branched-chain thiols as sulfur sources, were reported for the first time as precatalysts for eCO2RR to formate. Systematic material characterization demonstrated that Bi4Cl2S5 can undergo in-situ evolution into Bi2O2CO3 nanowires, serving as the genuine electrocatalyst for eCO2RR. Through the fine-tuning of ligands during the synthesis of Bi4Cl2S5 nanowires, the optimized Bi4Cl2S5-derived Bi2O2CO3 nanowires exhibited a maximum formate Faradaic efficiency (FEformate) of 95.3 % in eCO2RR using a traditional H-cell, surpassing other prepared samples. Furthermore, an FEformate of over 92.9 % was achieved in a wide potential window of 500 mV, and high performance was maintained over 20 h. This outstanding performance is attributed to the high intrinsic activity, accelerated charge transfer, and the large electrochemical active surface area associated with the characteristic sub-10 nm diameter nanowire structure. Moreover, density function theory calculations further revealed that Bi2O2CO3 can reduce the energy barriers for the formation of *OCHO intermediate and bolster formate production. Our work provides a novel synthesis strategy for excellent Bi-based catalysts in electrocatalysis.