Engineering membranes for molecular separation in organic solvents is still a big challenge. When the selectivity increases, the permeability tends to drastically decrease, increasing the energy demands for the separation process. Ideally, organic solvent nanofiltration membranes should be thin to enhance the permeant transport, have a well-tailored nanoporosity and high stability in harsh solvents. Here, we introduce a trianglamine macrocycle as a molecular building block for cross-linked membranes, prepared by facile interfacial polymerization, for high-performance selective separations. The membranes were prepared via a two-in-one strategy, enabled by the amine macrocycle, by simultaneously reducing the thickness of the thin-film layers (<10 nm) and introducing permanent intrinsic porosity within the membrane (6.3 Å). This translates into a superior separation performance for nanofiltration operation, both in polar and apolar solvents. The hyper-cross-linked network significantly improved the stability in various organic solvents, while the amine host macrocycle provided specific size and charge molecular recognition for selective guest molecules separation. By employing easily customized molecular hosts in ultrathin membranes, we can significantly tailor the selectivity on-demand without compromising the overall permeability of the system.
Hydroxyl functionalized polytriazole-co-polyoxadiazole (PTA-POD) copolymers have been synthesized and cast as promising highly thermally stable, chemically resistant, and antiorganic/biological fouling porous substrates for the fabrication of thin-film composite (TFC) forward osmosis (FO) membranes. The roles of PTA/POD ratios in the membrane substrates, TFC layers, and FO membrane performance have been investigated. This study demonstrates that the substrate fabricated from the copolymer containing 40 mol % PTA is optimal for the TFC membranes. Compared to the POD-TFC membrane, the 40 mol % PTA-TFC membrane exhibits a remarkable decrease in structural parameter (S) of more than 3.3 times. In addition, the 40 mol % PTA-TFC membrane is characterized by high water fluxes of 24.9 LMH and 47.2 LMH using 1 M NaCl as the draw solution and DI water as the feed under FO and pressure retarded osmosis (PRO) modes, respectively. Compared to a polysulfone (PSU) supported TFC-FO membrane under similar fabrication conditions, the 40% mol PTA-TFC membrane shows better FO performance and enhanced antifouling properties on the support (lower protein binding propensity and improved bacterial inhibition). Moreover, the performance of the 40 mol % PTA supported TFC-FO membrane can be improved to 37.5 LMH (FO mode)/78.4 LMH (PRO mode) and potentially higher by optimizing the support morphology, the TFC formation, and the post-treatment process. Hence, the use of newly developed hydroxyl functionalized polytriazole-co-polyoxadiazole copolymers may open up a new class of material for FO processes.
The preparation of crosslinked membranes with a zwitterionic structure based on a facile reaction between a newly synthesized copolyazole with free OH groups and (3-glycidyloxypropyl)trimethoxysilane (GPTMS) is reported. The new OH-functionalized copolyazole is soluble in common organic solvents, such as tetrahydrofuran (THF), dimethylsulfoxide (DMSO), N,N'-dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP) and can be easily processed by phase inversion. After crosslinking with GPTMS, the membranes acquire high solvent resistance. We show the membrane performance and the influence of the crosslinking reaction conditions on the thermal stability, surface polarity, pore morphology, and solvent resistance. By using UV-spectroscopy we monitored the solvent resistance of the membranes in four aggressive solvents (THF, DMSO, DMF and NMP) for 30 days. After this time, only minor changes (less than 2%) were detected for membranes subjected to a crosslinking reaction for 6 hours or longer. Our data suggest that the novel crosslinked membranes can be used for industrial applications in wide harsh environments in the presence of organic solvents.
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