Highly Flexible and Self‐Standing Covalent Organic Framework–Metal–Organic Framework (COF–MOF) Composite Crystalline Porous Material (CPM) Membrane for Molecular Separation

Abstract

AbstractCrystalline porous materials (CPMs), including covalent organic frameworks (COFs) and metal–organic frameworks (MOFs), are promising materials for advanced separation technologies. However, the challenge of transforming nanoscale CPMs into large‐area functional membranes hinders their application in the membrane separation process. Herein, a self‐standing pure COF (TpPa‐1) nanofiber membrane with high crystallinity, good flexibility, excellent mechanical properties, and scalability is prepared using an electrospinning process and polymer sacrificial template strategy. Subsequently, the COF nanofiber membrane is innovatively used to replace traditional inorganic discs, metal meshes, and polymer membranes as porous supports, and the COF–MOF composite CPM membrane is prepared through the tailorable and confined growth of zeolite imidazolium salt frame‐8 (ZIF‐8) on the surface of the COF membrane and in the gaps of the COF nanofibers. The COF–MOF composite membrane exhibits excellent permeability and significantly enhances separation selectivity for organic dyes. Moreover, MOF and COF form an interpenetrating network structure, and their similar chemical properties improve the interfacial stability between the two phases, giving the COF–MOF composite membrane good long‐term separation performance. This is the first self‐standing composite CPM membrane with excellent molecular sieving performance, which provides new insights into the design of high‐performance and robust composite membranes.