Double-Crosslinked H-PAN/MoS2/PEI Composite Nanofiltration Membrane for Ethanol Systems: Fabrication and Dye Separation Performance

Organic solvent nanofiltration (OSN) is a promising technology for solute removal from organic media, yet developing membranes with stable separation performance remains challenging. This study presents a solvent-resistant double-crosslinked nanofiltration membrane fabricated via a two-step strategy: preparation of the membrane by the polyion complexion reaction-assisted non-solvent-induced phase inversion (PIC-assisted NIPS) method and then post-crosslinking with hydrothermal treatment followed by quaternization with 1,3,5-tris(bromomethyl)benzene (TBB). To enhance solvent stability, molybdenum sulfide (MoS2) nanosheets were incorporated into a hydrolyzed polyacrylonitrile (H-PAN) substrate. The H-PAN/MoS2/PEI base membrane was fabricated by PIC-assisted NIPS with a polyethylenimine (PEI) aqueous solution as the coagulation bath. The membrane subsequently underwent dual crosslinking comprising hydrothermal treatment and 1,3,5-tris(bromomethyl)benzene (TBB)-mediated quaternization crosslinking, ultimately yielding the H-PAN/MoS2/PEI (Ther.+TBB QCL) composite membrane. These crosslinking procedures reduced the membrane’s separation skin layer thickness from 64 nm (uncrosslinked) to 41 nm. The resultant membrane effectively separated dyes from ethanol, achieving a rejection rate of 97.0 ± 0.9% for anionic dyes (e.g., Congo Red) and a permeance flux of 23.6 ± 0.2 L·m−2·h−1·bar−1 at 0.4 MPa. Furthermore, after 30 days of immersion in ethanol at 25 °C, its flux decay rate was markedly lower than that of a non-crosslinked control membrane. The enhanced separation performance and stability are attributed to the thermal crosslinking promoting amide bond formation and the TBB crosslinking introducing quaternary ammonium groups. This double-crosslinking strategy offers a promising approach for preparing high-performance OSN membranes.