Abstract
Alkaline hydrogen peroxide (H(2)O(2)) is highly desirable for critical applications due to its superior stability and reactivity, but it is incompatible with conventional near-neutral production methods. While covalent organic frameworks (COFs) show promise for photocatalytic H(2)O(2) generation, their alkaline performance is severely limited by poor charge dynamics and inadequate hydrophilicity, hindering the essential 2e(-) oxygen reduction reaction (ORR: O(2) + 2e(-) + H(2)O → HO(2) (-) + OH(-)) and 4e(-) water oxidation reaction (WOR: 4OH(-) → O(2) + 2H(2)O + 4e(-)). This work pioneers a dual-engineering strategy (molecular orbital and interfacial hydrogen-bonding network engineering) within β-ketoenamine-linked COFs to overcome these challenges simultaneously. By contrasting phenazine-based (TP-PZ-COF) and anthracene-based (TP-AN-COF) COFs, we demonstrate that strategic integration of sp(2)-N heteroatoms modulates molecular orbitals and enhances n → π* transitions, optimizing charge separation and transport for efficient 2e(-) ORR and 4e(-) WOR. Concurrently, the planar phenazine units form robust hydrogen-bonding networks that dramatically boost hydroxide ion (OH(-)) affinity and interfacial enrichment, thereby accelerating the 4e(-) WOR kinetics. This integrated approach enabled TP-PZ-COF to achieve an exceptional alkaline H(2)O(2) production rate of 4961 µmol g(-1) h(-1) in 0.01 M NaOH, representing an 8.1-fold increase over TP-AN-COF (606 µmol g(-1) h(-1)). The generated H(2)O(2) efficiently degraded industrial dye pollutants. Direct experimental and theoretical validations confirmed the cooperative mechanism between charge dynamics optimization and OH(-) affinity enhancement, providing a new blueprint for designing on-demand alkaline H(2)O(2) photocatalysts.