Covalent organic frameworks (COFs) have been rapidly applied in photocatalytic H₂O₂ production owing to their strong light absorption, suitable band structure, etc. However, sluggish water oxidation reaction (WOR) with low selectivity restricts the H₂O₂ photosynthesis efficiency of COFs. Herein, a thioether-decorated triazine-based COF (TDB-COF) was designed and developed for efficient overall H₂O₂ photosynthesis. TDB-COF achieves a photocatalytic H₂O₂ production rate of 723.5 μmol g⁻¹ h⁻¹ without any sacrificial agents and exhibits remarkable cyclic stability. The modification of thioether groups broadens the visible light absorption of TDB-COF and narrows its optical band gap. Such a strategy can not only effectively regulate the band structure suitable for two-electron two-steps WOR but also promote the photogenerated carriers transfer and accelerate a two-electron two-steps oxygen reduction process to generate H₂O₂, thus ultimately boosting the overall H₂O₂ photosynthesis. This work provides valuable suggestions for the development of the functional COFs towards overall H₂O₂ photosynthesis.

共价有机骨架材料(COFs)由于具有强吸光性、合适的能带结构等优点，已迅速应用于光催化H ₂ O ₂生产中。然而，选择性低的缓慢的水氧化反应（WOR）限制了COFs的H ₂ O _{2光合作用效率。}在此，设计和开发了一种硫醚修饰的三嗪基 COF (TDB-COF)，以实现高效的整体 H ₂ O ₂光合作用。TDB-COF 实现了723.5 μmol g ⁻¹ h ^{−1的光催化 H} ₂ O ₂生产率没有任何牺牲剂，并表现出显着的循环稳定性。硫醚基团的修饰扩大了 TDB-COF 的可见光吸收并缩小了其光学带隙。这种策略不仅可以有效调节适合双电子两步WOR的能带结构，还可以促进光生载流子转移，加速双电子两步氧还原过程生成H 2 O 2 _，​​从而_最终提高总的H ₂ O ₂光合作用。_{这项工作为开发用于整体 H 2} O ₂光合作用的功能性 COF 提供了有价值的建议。