Ultramicroporous cardo-pendant polyamide nanofilms for enhanced organic solvent nanofiltration

Permeable, selective, and stable polymeric membranes are essential for efficient molecular separation in organic solvents. Polymers of intrinsic microporosity (PIMs) with rigid and twisted chain structures offer abundant pores for high solvent permeability and are emerging as an ideal membrane material. However, guaranteeing high separation selectivity and stability is challenging owing to the wide pore size distribution and low swelling resistance in organic solvents. In this work, we developed intrinsically microporous polyamides (PAs) with cardo-pendant groups to create crosslinking, ultrathin, and defect-free nanofilms for organic solvent nanofiltration. The molecular simulation confirmed the pivotal role of cardo-pendant group structures in the amine monomers and exhibited their effect in creating pore channel structures within the PAs. Distinctive rigid fluorenyl-based cardo-pendant groups were introduced in amine monomers to finely tailor the packing of PA chains for high microporosity and a finely tuned pore size. We further achieved the growth of such PAs using a cyclic deposition strategy, in-situ generating highly crosslinking nanofilms with an ultralow thickness of 23–36 nm without structure relaxation. As such, the typically-designed PA membranes demonstrated high and stable solvent permeance (e.g., 18 L m–2 h–1 bar–1 for methanol) and high solute rejection (up to 95% rejection of 306 Da Azure I), which is superior to its counterparts and current PIM membranes, presenting a new perspective for efficient organic solvent nanofiltration.