Bisite Sulfonate-Functionalized Covalent Organic Frameworks with Efficient and Dynamic Proton Transportation for Accelerating H2O2 Photosynthesis
K. Yang, L. Chen, K. Xiong, J. Yang, M. Adeli, S. Li, M. Wang, C. Cheng, C. Zhao – 2025
Photocatalytic hydrogen peroxide (H2O2) production using covalent organic frameworks (COFs) relies on the concerted operation of two half-reactions: oxygen reduction (ORR) and water oxidation (WOR). A critical limitation arises from the frequent proton and O2 supply-demand imbalance between these processes, which constrains overall H2O2 yields. To address this challenge, a bisite sulfonate-functionalized COF (2-SO3H-COF) is developed that serves as an efficient proton mediator, promoting both solution-phase proton/O2 uptake and rapid intraframework proton transport through hopping mechanisms. The optimized material demonstrates remarkable performance, yielding 4744 µmol g−1 h−1 H2O2 under acidic conditions (pH = 1) and even achieving 11 470 µmol g−1 h−1 in 10% benzyl alcohol solution, which represents a 3.36-fold enhancement over unmodified COFs in deionized water. Isotopic labeling and computational studies elucidate how -SO3H groups facilitate proton conduction from water into the framework while enhancing O2 adsorption, thereby promoting a direct 2e− ORR pathway. When implemented in a flow reactor system, 2-SO3H-COF enables continuous H2O2 production while simultaneously degrading >95% of organic dyes and maintaining 99% antibacterial efficacy. These findings establish a general design principle for proton-regulating photocatalysts and expand the potential of COF materials for sustainable chemistry and environmental applications.
