Dual-pore covalent organic frameworks (COFs) offer a molecular scaffold for introducing building blocks into periodically organized polygonal skeletons to produce fascinating structural features. The rapid development of this material has attracted intensive interest from researchers with diverse expertise. This review selects the leading scientific findings about dual-pore COFs and highlights their functions and perspectives on design, structure properties, and synthesis strategies. Dual-pore COFs, as newly hetero-pore COFs by integrating particular pores into one polygonal skeleton, have been compared to conventional COFs. Dual-pore COFs display hierarchical/heterogeneous porosities and homogeneous porosity, which endow them with exceptional features involving mass diffusion, charge transfer, and large surface area with abundant active sites. Additionally, the strategic dual-pore design by opting for different approaches, such as integration of [D2h + C2] symmetries, kagome-type lattices, and other symmetric arrangements of monomers, are inclusively discussed. Identification and construction of dual-pores in COFs via optimal synthetic methods, such as desymmetrization, multiple linking sites, and orthogonal reactions, are highlighted as the primary pore engineering routes to simultaneously regulate the growth and alter the characteristics of COFs for promising applications. Lastly, a focused discussion on various challenges and critical fundamentals of dual-pore engineering is successfully outlined, with potential prospects of introducing dual-pore in COFs.
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