Hierarchically Porous Covalent Organic Frameworks: Synthesis Methods and Applications

Abstract Covalent organic frameworks (COFs) with high porosity have garnered considerable interest for various applications owing to their robust and customizable structure. However, conventional COFs are hindered by their narrow pore size, which poses limitations for applications such as heterogeneous catalysis and guest delivery that typically involve large molecules. The development of hierarchically porous COF (HP‐COF), featuring a multi‐scale aperture distribution, offers a promising solution by significantly enhancing the diffusion capacity and mass transfer for larger molecules. This review focuses on the recent advances in the synthesis strategies of HP‐COF materials, including topological structure design, in‐situ templating, monolithic COF synthesis, defect engineering, and crystalline self‐transformation. The specific operational principles and affecting factors in the synthesis process are summarized and discussed, along with the applications of HP‐COFs in heterogeneous catalysis, toxic component treatment, optoelectronics, and the biomedical field. Overall, this review builds a bridge to understand HP‐COFs and provides guidance for further development of them on synthesis strategies and applications.