Stepwise Protonation of Three‐Dimensional Covalent Organic Frameworks for Enhancing Hydrogen Peroxide Photosynthesis

Abstract Three‐dimensional covalent organic frameworks (3D COFs), recognized for their tailorable structures and accessible active sites, offer a promising platform for developing advanced photocatalysts. However, the difficulty in the synthesis and functionalization of 3D COFs hinders their further development. In this study, we present a series of 3D‐ bcu ‐COFs with 8 connected porphyrin units linked by linear linkers through imine bonds as a versatile platform for photocatalyst design. The photoresponse of 3D‐ bcu ‐COFs was initially modulated by functionalizing linear linkers with benzo‐thiadiazole or benzo‐selenadiazole groups. Furthermore, taking advantage of the well‐exposed porphyrin and imine sites in 3D‐ bcu ‐COFs, their photocatalytic activity was optimized by stepwise protonation of imine bonds and porphyrin centers. The dual protonated COF with benzo‐selenadiazole groups exhibited enhanced charge separation, leading to an increased photocatalytic H 2 O 2 production under visible light. This enhancement demonstrates the combined benefits of linker functionalization and stepwise protonation on photocatalytic efficiency.