Interfacial cross-linking was used to prepare composite organic solvent nanofiltration (OSN) membranes comprising a polydopamine (PDA) active layer formed on a polybenzimidazole (PBI) substrate. Dibromo-p-xylene (DBX) was employed as a cross-linking agent to make the composite membranes chemically stable against harsh polar aprotic solvents. The interfacial cross-linking of PDA/PBI allowed for finely tuning the molecular weight cutoff (MWCO) of the membrane, resulting in a membrane with precise molecular separation capabilities for OSN. The morphology and surface properties of the membranes were characterized, and a membrane with a MWCO of 286 Da was investigated for OSN of a series of solvents. The membrane permeance was in the order of acetonitrile (MeCN) > methanol (MeOH) > acetone > toluene > dimethylformamide (DMF) > heptane > ethanol (EtOH) > isopropanol (IPA) > tetrahydrofuran (THF). The membranes displayed a sharp pore size distribution, yielding a rejection rate of over 99% for Rose Bengal (RB, MW 1020 g/mol) and Remazol brilliant blue (RBB, MW 626.5 g/mol) from DMF and EtOH solutions. When it came to methyl orange (MO, MW 327.3 g/mol) that had a molecular weight closer to the MWCO of the membrane, the membrane still displayed a high rejection rate of 95% and 99% in nanofiltrating solvents DMF and EtOH, respectively. In addition, it was demonstrated that the membrane was able to effectively fractionate mixed solutes having molecular weights appropriate for the MWCO rating of the membrane during OSN.
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