Precisely Regulating the Interface Bi−S Bond to Enhance the Rapid Charge Transfer Kinetics from the Active Site to Key Reaction Intermediates during CO ₂ Photoreduction

The carbon dioxide reduction reaction involves a series of consecutive intermediate reaction processes. How to precisely control the charge dynamics between the catalyst and the intermediate products and achieve the rapid migration of electrons remains a challenge. In this work, Bi defects were introduced through a simple hydrothermal method. The defect structure disrupts the periodicity of the crystal lattice, causing the length of the Bi−S bonds at the interface to shorten. The optimized Bi−S bond length enabled Biv-Bi2S3/ZnS to have faster electron transfer kinetics, significantly enhancing the electron coupling ability between the catalyst and the reduction intermediate, with the conversion kinetics of the key intermediate *CHO increasing by 10.8 times. The combination of experimental data and density functional theory calculations indicates that this interfacial short-range transfer path can enable the rapid participation of electrons in the reaction process, thereby improving the photocatalytic reduction performance.