Nanoscale 0D/1D Heterojunction of MAPbBr₃/COF Toward Efficient LED-Driven S-S Coupling Reactions

Precise and efficient management of disulfide bonds will offer multiple merits for the development of organosulfur chemistry, pharmacology, and life sciences. However, the current S-S coupling synthesis strategy encounters bottlenecks in conforming to efficient separation of products, which limits its industrial-scale application. In view of the superoxide radical-triggered reaction mechanism of S-S coupling, this study demonstrates a multifunctional in situ-assembled 0D/1D S-scheme heterojunction photocatalyst (MAPB-T-COF) constructed by MAPbBr(3) quantum dots and imine covalent organic framework (COF) nanowires under the guidance of band engineering management. MAPB-T-COF exhibits a superior photocatalytic performance in the conversion of 4-methylbenzenethiol (4-MBT) to p-tolyl disulfide (PTD) under blue LED illumination. Specifically, it achieves an impressive 100% yield with a record photon quantum efficiency as high as 12.76%, as well as universal availability for various derivatives, rivaling all the incumbent similar reaction systems. This study not only highlights the effectiveness and merits of nanoscale S-scheme heterojunction photocatalysis for the S-S coupling reaction but also achieves a perfect trade-off between high quantum efficiencies and strong chemical redox potentials. In addition, the free radical that triggers the reaction was monitored in situ by an electron paramagnetic resonance (EPR) instrument, which provided meaningful insights into the reaction mechanism. This study may inspire the development of photoelectric conversion devices, photoelectrodes, and photocatalysts utilizing nanoscale, low-dimensional heterojunctions.