Enhanced Mg2+/Li+ separation performance of polyelectrolyte multilayers nanofiltration membranes modified by trimethylamine N-oxide zwitterions

Abstract

Polyelectrolyte multilayer nanofiltration (NF) membranes have garnered attention for their potential in Mg2⁺/Li⁺ separation applications, particularly due to their positively charged nature and the versatility offered by the layer-by-layer (LbL) self-assembly technique. However, these membranes often face significant challenges in balancing high ion selectivity with adequate water permeability. Addressing these limitations, this study introduces a novel approach by grafting a zwitterionic material, trimethylamine N-oxide (TMAO), onto polyacrylamide hydrochloride (PAH), creating a new cationic polyelectrolyte (TPAH). By cyclically depositing sodium polystyrene sulfonate (PSS) and TPAH onto a polyethersulfone (PES) substrate, we have successfully fabricated a high-performance NF membrane (i.e., (PSS/TPAH)n) that demonstrates enhanced Mg2⁺/Li⁺ selectivity with high water permeability. TMAO features shorter distances between its positive and negative charge groups and smaller dipoles compared to other zwitterions. These characteristics enhance its ability to resistance to salt effects and transfer charge from amine oxide to water molecule. Furthermore, the grafting of TMAO enhanced the hydrophilicity of TPAH and regulated the charge distribution of the polyelectrolyte. Compared to the control membrane (PSS/PAH)n, the optimized membrane (PSS/TPAH)n showed reduced rejection of LiCl from 60.9 ± 2.7 % to 35.9 ± 1.5 %, while that of MgCl2 increased from 94.3 ± 1.6 % to 96.1 ± 0.7 %. Additionally, water permeability improved from 9.2 ± 0.9 LMH/bar to 16.1 ± 0.5 LMH/bar. Notably, the membranes exhibited an improved selectivity for Mg2+/Li+ ions in synthetic saline, reaching a maximum of 30.5 ± 1.5, highlighting its potential for practical separation applications. Density functional theory simulations indicate that TMAO not only enhances Donnan effect and intensify ion dehydration of polyelectrolyte multilayers NF membranes but also increases their hydrophilicity. In general, these polyelectrolyte multilayers NF membranes exhibit considerable promise for multiple applications, such as seawater pretreatment, groundwater softening and lithium extraction.