Construction of supramolecular S-scheme heterojunctions assisted by hydrogen bond subtle-tuning actuates highly efficient photocatalytic oxidation

Controllable fine-tuning of heterojunction interfaces at the atomic level represents a promising strategy for enhancing semiconductor photocatalytic performance. Herien, we propose a strategy to introduce hydrogen-bonded electron channels at the heterojunction interface to achieve rapid interfacial electron transfer. This S-scheme hydrogen-bonded supramolecular self-assembled H12SubPcB-OPhCH2COOH/Ag3PO4 semiconductor heterojunction exhibits efficient and stable photocatalytic degradation of a wide range of pharmaceuticals and personal care products. Experimental results and theoretical simulations demonstrate that the interface O-H⋅⋅⋅O hydrogen bond at the heterojunction generates an internal electric field, which provides the driving force for accelerated S-scheme charge transfer and enhanced redox properties. Furthermore, the combination of TDDFT calculations and synchronous illumination XPS has revealed that hydrogen bonding acts as a suction electron pump in the excited state, transferring electrons from Ag3PO4 to SubPc-2. These findings suggest that hydrogen-bonded supramolecular semiconductor can be used to develop high-performance photocatalytic materials for environmental remediation.