Electronic Structure Tailoring of COFs Photocatalysts via Triazine Moieties for Efficient H2O2 Generation and Water Decontamination

• • FB-AT achieves a H2O2 production rate of 11055 μmol g-1 h-1 in pure water, surpassing most reported COF photocatalysts by an order of magnitude, which directly translates to reduced reactor footprint and lower operational costs for on-site H2O2 generation. • • Solar-to-chemical conversion efficiency reaches 1.16%, a benchmark that enables economically viable solar-driven H2O2 production, potentially displacing the energy-intensive anthraquinone process in small-scale decentralized applications. • • Complete degradation of phenol, tetracycline, and rhodamine B occurs within 5–15 min under visible light irradiation, demonstrating rapid pollutant mineralization kinetics essential for industrial wastewater treatment with hydraulic retention times under 20 minutes. • • The triazine moiety spatial arrangement lowers the thermodynamic energy barrier for *OOH intermediate formation, as confirmed by theoretical calculations, providing a design rule for engineering COFs with enhanced oxygen reduction reaction activity and suppressed exciton binding energy.