Tailoring pore microenvironments in scalable classic COFs boosts solar H₂O₂ production and antibiotic remediation

Covalent organic frameworks (COFs) are promising for solar-driven chemical synthesis and environmental remediation, yet their practical application is constrained by the trade-off between structural sophistication and synthetic scalability. In this work, we develop a pore microenvironment engineering strategy on classic COF skeletons to boost photocatalytic performance without relying on intricate monomer design. Two isostructural hexagonal COFs (TTA-DMA and TTA-DHA) are synthesized via a facile, cost-effective autoclave solvothermal route using commercially available linkers, achieving gram-scale yield while preserving high crystallinity and uniform pore channels. Combined advanced transient spectroscopies and density functional theory calculations demonstrate that hydroxyl functionalization on pore walls rationally modulates localized electronic states, extending light harvesting, suppressing radiative charge recombination, accelerating charge separation, and lowering the O₂ activation energy barrier. The optimized TTA-DHA delivers an exceptional solar H₂O₂ production rate of 14,562 mmol g⁻¹ h⁻¹ with an apparent quantum yield of 9.1% at 400 nm. The in situ generated H₂O₂ further drives a concurrent advanced oxidation cascade, achieving 85%-97% degradation of five representative recalcitrant antibiotics within 1 h under visible light. This work bridges scalable material fabrication with efficient solar energy conversion, providing a practical blueprint for functionalizing classic porous frameworks toward multipurpose applications.