Ultrafast Interfacial Self‐Assembly toward Bioderived Polyester COF Membranes with Microstructure Optimization

Abstract The precise manipulation of the microstructure (pore size, free volume distribution, and connectivity of the free‐volume elements), thickness, and mechanical characteristics of membranes holds paramount significance in facilitating the effective utilization of self‐standing membranes. In this contribution, the synthesis of two innovative ester‐linked covalent–organic framework (COF) membranes is first reported, which are generated through the selection of plant‐derived ellagic acid and quercetin phenolic monomers in conjunction with terephthaloyl chloride as a building block. The optimization of the microstructure of these two COF membranes is systematically achieved through the application of three different interfacial electric field systems: electric neutrality, positive electricity, and negative electricity. It is observed that the positively charged system facilitates a record increase in the rate of membrane formation, resulting in a denser membrane with a uniform pore size and enhanced flexibility. In addition, a correlation is identified wherein an increase in the alkyl chain length of the surfactants leads to a more uniform pore size and a decrease in the molecular weight cutoff of the COF membrane. The resulting COF membrane exhibits an unprecedented combination of high water permeance, superior sieving capability, robust mechanical strength, chemical robustness for promising membrane‐based separation science and technology.