Dual-phase microporous polymer nanofilms by interfacial polymerization for ultrafast molecular separation

Fine-tuning microporosity in polymers with a scalable method has great potential for energy-efficient molecular separations. Here, we report a dual-phase molecular engineering approach to prepare microporous polymer nanofilms through interfacial polymerization. By integrating two micropore-generating units such as a water-soluble Tröger's base diamine (TBD) and a contorted spirobifluorene (SBF) motif, the resultant TBD-SBF polyamide shows an unprecedentedly high surface area. An ultrathin TBD-SBF membrane (~20 nm) exhibits up to 220 times improved solvent permeance with a moderate molecular weight cutoff (~640 g mol^-1) compared to the control membrane prepared by conventional chemistry, which outperforms currently reported polymeric membranes. We also highlight the great potential of the SBF-based microporous polyamides for hydrocarbon separations by exploring the isomeric effects of aqueous phase monomers to manipulate microporosity.