Accelerated oxygen activation over uranyl decorated covalent organic framework for universally promoted H2O2 photosynthesis

• • Uranyl decoration on imine-based COFs boosts H2O2 production by 1.6–10.1 folds across pH 2–11, with optimal rate of 1435.9 μmol g−1 h−1 (28.72 mmol g(U)−1 h−1) under visible light, demonstrating universal pH applicability for industrial wastewater treatment. • • The enhanced performance stems from accelerated oxygen activation and favored formation of ·O2− and *OOH intermediates, facilitating the two-step single-electron ORR, which is critical for selective H2O2 synthesis. • • The optimal catalyst, uranyl-decorated TTa-COF, achieves a high space-time yield of 28.72 mmol per gram of uranium per hour, indicating efficient use of uranium as a cocatalyst, which is economically relevant for precious metal replacement. • • The work provides a new strategy for designing uranyl-based photocatalysts, expanding the application of uranium chemistry beyond nuclear energy, with potential for scalable solar-driven H2O2 production.