Deep removal the irreversible contaminants of N-MnOx@PVDF membrane using in-situ coupling catalyzed ozonation

Due to high efficiency and durability, Polyvinylidene Fluoride (PVDF) membranes are promising for their application in wastewater purification. However, they still inevitably face the challenge of membrane clogging problem, restricting separation and anti-fouling performance. Herein, a novel N-MnO x @PVDF membrane with high catalytic ozonation ability was synthesized using the blending non-solvent-induced reverse transfer method, evidenced by X-ray diffraction, Fourier transform infrared spectrometer, and X-ray photoelectron spectroscopy. Compared with pristine PVDF, N-MnO x @PVDF has better hydrophilicity and reasonable pore structure, resulting in higher permeability and anti-fouling properties. After in-situ catalytic ozonation cleaning, the Flux Recovery Ratio ( FRR ) increases from 72.1% to 99.8%, and the irreversible pollution rate ( R ir ) decreases from 31.9% to 0.13%. Meanwhile, the high stability and reusability can be demonstrated from high Total Organic Carbon (TOC) removal efficiency of humic acid (HA, 93%), high FRR (94%), and low R ir (4.3%) after consecutive cycles filtration experiments. In addition, further mechanistic insights are verified by 3D-excitation Emission Matrices (EEM) and Electron Paramagnetic Resonance (EPR) characterization, demonstrating that the removal of irreversible contaminants can be mainly ascribed to indirect oxidation of 1 O 2 , and their possible generation pathway is also proposed. This study provides valuable insights into the development of advanced antifouling membranes.