MnFe2O4 composited polyvinylidene fluoride catalytic ultrafiltration membrane via peroxymonosulfate activation for humic acid treatment: Exploration of synergistic mechanisms

Membrane separation has become the most promising technology in the field of wastewater purification, but there will inevitably be membrane fouling. Catalytic polymer membranes combining membrane filtration and advanced oxidation technologies (AOPs) offered an alternative for mitigating membrane fouling. This work successfully synthesized a MnFe2O4 catalytic polyvinylidene fluoride (MnFe2O4-PVDF) ultrafiltration membrane and systematically investigated the performance of peroxymonosulfate (PMS)/MnFe2O4 membrane oxidation filtration system for removing humic acid (HA). The results showed that the PVDF@MnFe2O4/PMS synergistic system oxidized HA into small molecules and further repelled them to the membrane surface by size exclusion to form a filter cake layer. The PVDF@MnFe2O4/PMS system exhibited the lowest irreversible fouling (0.414 × 1010m−1) and the highest HA removal efficiency (83.4 %) compared with PVDF single filtration. After hydrodynamic cleaning, PVDF@MnFe2O4 can achieve 73.2 % water flux recovery. The membrane fouling mitigation mechanisms were investigated by the Extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory and the combined pore blockage-cake filtration model. Quenching experiment and density functional theory calculation (DFT) revealed the HA degradation as a result of the synergistic action of free radicals (SO4⋅-, ⋅OH) and non-free radicals(1O2) in PVDF@MnFe2O4/PMS system. Additionally, we evaluated the effectiveness of the system in the removal of natural organic matter (NOM) from surface water. The results suggested that the PVDF@MnFe2O4/PMS system could validly remove the main fluorescent matters from surface water. In conclusion, this work provides a promising route for solving the membrane fouling caused by NOM in water.