Internal electric field engineering step-scheme-based heterojunction using lead-free Cs3Bi2Br9 perovskite-modified In4SnS8 for selective photocatalytic CO2 reduction to CO

This study focuses on improving photocatalytic CO2 reduction reaction (CRR) activity and modulating product selectivity. An In4SnS8/Cs3Bi2Br9-X (ISS/CBB-X) heterojunction is prepared using novel lead-free Cs3Bi2Br9 perovskite quantum dot-modified In4SnS8, which shows considerable potential as photocatalysts for CRRs under visible light. The optimised ISS/CBB photocatalyst exhibits high activity and CO selectivity with a CO yield and selectivity of 9.55 mu mol g(-1) h(-1) and 92.9%, respectively, 3.8 and 1.5 times higher than those of pristine ISS, respectively. Moreover, the step-scheme (S-scheme) mechanism can be fully confirmed via in situ irradiated X-ray photoelectron spectroscopy, in situ electron spin resonance, femtosecond time-resolved absorption spectroscopy and density functional theory calculations. Based on in situ diffuse reflectance spectra and theoretical investigations, the ISS/CBB shows a decreased energy barrier towards CO2 reduction to CO through an adsorbed *COOH intermediate. This study contributes to the further understanding of fabricating efficient S-scheme-based photocatalysts for selective CRR.

Automated summary

This study focuses on improving the activity of the photocatalytic CO2 reduction reaction and modulating product selectivity. The In4SnS8/Cs3Bi2Br9-X heterojunction shows high CO yield and selectivity, with improved performance compared to the pristine In4SnS8 catalyst. The S-scheme mechanism is confirmed through various experimental and theoretical techniques, providing insights into the improved efficiency of selective CO2 reduction to CO.