Zn2+-Mediated Co-Deposition of Dopamine/Tannic Acid/ZIF-8 on PVDF Hollow Fiber Membranes for Enhanced Antifouling Performance and Protein Separation

The inherent hydrophobicity of poly(vinylidene fluoride) (PVDF) ultrafiltration membranes leads to severe membrane fouling when processing proteinaceous solutions and organic contaminants, significantly limiting their practical applications. This study presents a novel metal-ion mediated co-deposition strategy for fabricating high-performance antifouling poly(vinylidene fluoride) (PVDF) hollow fiber ultrafiltration membranes. Through Zn²⁺ coordination-driven self-assembly, a uniform and stable composite coating of dopamine (DA), tannic acid (TA), and ZIF-8 nanoparticles was successfully constructed on the membrane surface under mild conditions. The modified membrane exhibited significantly enhanced hydrophilicity, with a water contact angle of 21° and zeta potential of -29.68 mV, facilitating the formation of a dense hydration layer that effectively prevented protein adhesion. The membrane demonstrated exceptional separation performance, achieving a pure water permeability of 771 L/(m²∙h∙bar) and bovine serum albumin (BSA) rejection of 97.7%. Furthermore, it showed outstanding antifouling capability with flux recovery rates exceeding 83.6%, 74.7%, and 71.5% after fouling by BSA, lysozyme, and ovalbumin, respectively. xDLVO analysis revealed substantially increased interfacial free energy and stronger repulsive interactions between the modified surface and protein foulants. The antifouling mechanism was attributed to the synergistic effects of hydration layer formation, optimized pore structure, additional water transport pathways from ZIF-8 incorporation, and electrostatic repulsion from negatively charged surface groups. This work provides valuable insights into the rational design of high-performance antifouling membranes for sustainable water treatment and protein separation applications.