Inwardly Directed Linker Propagation: Constructing 3D Covalent Organic Frameworks for Efficient H2O2 Photosynthesis

The limited design strategy of three‐dimensional covalent organic frameworks (3D COFs) greatly restricts their structural diversification and potential applications. Herein, we propose inwardly directed linker propagation strategy to targeted assemble of 3D COFs (COF‐IN‐1 and COF‐IN‐2), and comparing them with outwardly directed expanded COFs (COF‐OUT‐1 and COF‐OUT‐2). COF‐OUTs exhibits planar heteroporous 2D frameworks with cpt topology, while COF‐INs engineer controlled triple entanglements into networks, forming 3D framework with acs topology. Moreover, the COFs assembled via inwardly directed linker propagation effectively enhanced the production of H2O2 photosynthesis.To demonstrate the application potential, a biphasic fluid system was constructed for continuous H2O2photosynthesis and extraction. This work not only expands the design strategy for achieving 3D COFs, but also demonstrate that the dimensional regulation of frameworks and tuning of applications can arise from different expanding directions of the linkers.