Development of highly permeable and antifouling ultrafiltration membranes based on the synergistic effect of carboxylated polysulfone and bio-inspired co-deposition modified hydroxyapatite nanotubes.

Hybridization has become a powerful toolbox for developing ultrafiltration membranes with superior properties. However, it remains challenging to give full play to the utility of nanofillers because of poor bonding strength between polymers and inorganic nanomaterials. Herein, hydroxyapatite nanotubes (HANTs) were modified via bio-inspired polydopamine (PDA) and polyethylenimine (PEI) co-deposition. Meanwhile, polysulfone with carboxylation degree of 30% (PSF-COOH-30%) was synthesized by nucleophilic substitution reaction and employed as the membrane matrix. The results showed that when 0.3 wt% HANTs@PDA/PEI was incorporated, the pure water flux of the hybrid membrane achieved about 3.2 times that of the unfilled membrane and the rejection rate of bovine serum albumin (BSA) and humic acid (HA) remained 94.5% and 97.8%, respectively. Meanwhile, the flux recovery ratio for BSA and HA solutions (1 g/L) reached 90.8% and 93.7%, respectively. Specifically, the superiority of UF performance benefited from the synergistic effect of both the carboxylated polymer and the nanofiller. On one hand, the incorporation of HANTs@PDA/PEI promoted the formation of more porous membrane structure and improved the hydrophilicity of the membrane. On the other hand, due to the existence of COOH, the electrostatic repulsion between the membranes and contaminants enhanced the fouling resistance for BSA and HA. Conspicuously, the ease and versatility of co-deposition provide new ideas in the construction of nanohybrid and the favorable improvement renders that appropriate combination of polymer and additive is an effective way for developing future ultrafiltration membranes.