Sunlight-driven photosynthesis by covalent organic frameworks (COFs) from water and air without using sacrificial reagents is a promising H2O2 fabrication approach, but is still restricted by the insufficient charge separation and sluggish 2e- water oxidation process. Herein, we provide a facile strategy to simultaneously improve charge separation and water oxidation in COFs via confining the charge transfer pathways from two diversion ones to a confluence one through regulating the site of nitrogen in bipyridine. Combining in-situ characterization with computational calculations, we reveal that compared to COF-BD1 containing two diversion charge transfer pathways, the charge transfer pathway in COF-BD2 is confined to a confluence one due to the electron-deficiency effect of nitrogen, which greatly accelerates the intermolecular and out-of-plane charge transfer. Via effectively reducing the energy barrier of rate-determining water oxidation reaction, the subsequent water oxidation process to produce key *OH intermediate in COF-BD2 is also greatly facilitated, boosting the yield of H2O2 (5211 μmol g-1 h-1) from water, oxygen, and light without sacrificial agents or additional energy consumption. We further demonstrate that H2O2 can be efficiently produced by COF-BD2 in broad pH range, in real water, and in enlarged reactor with using natural sunlight for water decontamination.

The proliferation and spread of antibiotic-resistant bacteria (ARB) significantly threaten human health and ecosystem. Periodate (PI) based advanced oxidation process has potentials for water purification but limited by complex activators or activation process. Herein, we demonstrated that H2O2 could be used to activate PI, achieving efficient ARB disinfection performance. Particularly, we found that the PI/H2O2 system (0.1 mM for both oxidants) could inactivate ARB (Escherichia coli) within 35 min. The intracellular defense system attacked by HO· radicals generated in the disinfection system, resulting in the inactivation of ARB. Antibiotic resistance genes (ARGs) released with the lysis of cell membrane could be further degraded by HO· radicals. Moreover, we found that the PI/H2O2 system was effective to inactivate ARB in a broad range of ionic strengths, with coexisting common ions and humic acid, as well as in four typical actual water bodies. The PI/H2O2 system could also efficiently disinfect other types of bacteria and degrade typical organic contaminants. In addition, under sunlight irradiation, the ARB inactivation performance of the PI/H2O2 system could be greatly improved. This study provided a practical and efficient way for decontaminating ARB/ARGs-polluted water.