In situ hydrolyzed microporous polymer membranes for additional free volume to facilitate CO2 permeation

Advancements in membrane separation technology play a pivotal role in separation processes closely associated with the environment and energy. However, presently available commercial polymeric membranes encounter the challenge of low permeability, impacting both separation efficiency and membrane module costs. Here, we propose a simple and effective in situ acid hydrolysis strategy to significantly enhance membrane permeability. Specifically, a tetrafluorinated monomer with hydrolyzable Schiff base groups (TFNAD) has been meticulously designed, synthesized, and copolymerized with commercial TFTPN and TTSBI, yielding a series of copolymers. Subsequently, in situ hydrolysis removes aniline from the membrane, freeing up the occupied free volume and creating additional channels for gas transport. This process substantially enhances gas permeability while preserving the desired selectivity. PIM-TFAD-30 showed a 68 % improvement in CO2 permeability with virtually no compromise in CO2/N2 selectivity compared to the pre-hydrolysis membrane. Meanwhile, PIM-TFAD-30 also displayed outstanding separation performance and plasticization resistance in simulated flue gas tests, demonstrating its potential for practical application. This facile and straightforward hydrolysis method opens up a new perspective for preparing and modifying polymeric separation membranes beyond gas separation.