Dual-Reaction Pathway Engineering Leveraging Diphenylsulfone Units in Sulfone-Functionalized COFs for Solar-Driven Hydrogen Peroxide Production

Incorporating sulfone units into covalent organic frameworks (COFs) to construct a donor–acceptor (D–A) electronic structure provides a novel strategy for efficient photocatalytic hydrogen peroxide (H 2 O 2 ) synthesis by effectively modulating the optoelectronic properties and catalytic activity of the materials. However, the practical application of such materials still faces key challenges, including facile recombination of photogenerated charge carriers, limited interfacial mass transfer kinetics, and insufficient long-term operational stability. This study designed and synthesized two novel sulfone-based COFs (Sd-COFs and Bis-COFs), which innovatively employ ring-opened sulfone motifs as strong electron-accepting units, distinguishing it from conventional fused-ring sulfone structures. Both materials are capable of achieving efficient dual-pathway H 2 O 2 production via water oxidation and oxygen reduction under visible-light irradiation. The unique D–A architecture facilitates the separation and migration of photogenerated charges and enhances oxygen adsorption and activation, resulting in a high H 2 O 2 production rate of 5968.8 μmol·g –1 ·h –1 without any sacrificial agent. When benzyl alcohol is employed as a sacrificial agent, the production rate is markedly increased to 35,621.1 μmol·g –1 ·h –1, outperforming most reported organic photocatalysts. The in situ antibacterial assay further confirmed that the synthesized COFs possess a substantial actual antibacterial effect. After 1 h of light irradiation, Sd-COFs at a concentration of 1.5 mg·mL –1 achieved an antibacterial efficiency of 95.08% against E. coli . This work provides an effective design strategy for sulfone-containing COFs-based photocatalysts, while enabling efficient in situ antibacterial activity, thus offering a new perspective for the future development of green, efficient, and high-performance COFs-based photocatalytic systems.