Low Fouling Polyelectrolyte Layer-by-Layer Self-Assembled Membrane for High Performance Dye/Salt Fractionation: Sequence Effect of Self-Assembly.

Layer-by-layer (LbL) self-assembly of oppositely charged polyelectrolytes (PEs) is usually performed on a conventional ultrafiltration base substrate (negative zeta potential) by depositing a cationic PE as a first layer. Herein, we report the facile and fast formation of high performance molecular selective membrane by the nonelectrostatic adsorption of anionic PE on the polyvinylidene fluoride (PVDF, zeta potential -17 mV) substrate followed by the electrostatic LbL assembly. Loose nanofiltration membranes have been prepared via both concentration-polarization (CP-LbL, under applied pressure) driven and conventional (C-LbL, dipping) LbL self-assembly. When the first layer is poly(styrene sodium) sulfonic acid, the LbL assembled membrane contains free -SO 3 - groups and exhibits higher rejection of Na 2 SO 4 and lower rejection of MgCl 2 . The reversal of salt rejection occurs when the first layer is quaternized polyvinyl imidazole (PVIm-Me). The membrane (five layers) prepared by first depositing PStSO 3 Na shows higher rejection of several dyes (97.9 to >99.9%), higher NaCl to dye separation factor (52-1800), and higher dye antifouling performance as compared to the membrane prepared by first depositing PVIm-Me (97.5-99.5% dye rejection, separation factor ∼40-200). However, the C-LbL membrane requires a longer time of self-assembly or higher PE concentration to reach a performance close to the CP-LbL membranes. The membranes exhibit excellent pressure, pH (3-12), and salt (60 g L -1 ) stability. This work provides an insight for the construction of low fouling and high-performance membranes for the fractionation of dye and salt based on the LbL self-assembly sequence.