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Microporous polymers are uniquely attractive for membrane-mediated gas separations; however, conventional microporous polymers suffer a ubiquitous trade-off between gas permeability and selectivity, leading to bottlenecks in their practical applications. Functionalization of microporous polymers via molecule engineering is an effective way to enhance their gas separation performance and processability. This review outlines the research progress of ionization to improve the gas separation performance of typical microporous polymers (e.g., polymers of intrinsic microporosity (PIM), perfluorinated polymers, microporous polyimides, etc.) and summarizes the different ionization methods, including carboxylation, sulfonation, quaternization, and other ionization processes. Additionally, the review also explores the research progress of ionization to regulate the processability, microporosity, and gas separation properties of microporous polymers. Specifically, ionization can effectively tailor the microporosity, improve the solubility coefficients of gas molecules, especially CO 2 , and enhance gas selectivities. In addition, ionization can improve the processability of PIMs and enhance the membrane plasticization resistance. Ionic microporous polymers provide an essential platform for developing energy-efficient and high-performance gas separation membranes.

The implementation of synthetic polymer membranes in gas separations ranging from natural gas sweetening, hydrogen recovery, helium extraction, carbon capture, and oxygen/nitrogen enrichment etc., has stimulated vigorous development of high-performance...

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