The development of superwetting membranes is a promising approach for separating emulsified oily wastewater. However, challenges such as low flux without external pressure and membrane fouling have hindered membrane performance. Herein, we fabricated a novel nanofibrous membrane by grafting Co-doped Zr-UiO-66-NH2 (UiO(Zr/Co)) nanoparticles onto carboxylated cellulose nanocrystals (CCNC)-polyacrylonitrile (PAN) mixed matrix electrospinning membrane via chemical bonds through EDC/NHS reaction. CCNC served a dual purpose by enhancing membrane hydrophilicity and providing connection points for UiO(Zr/Co). The as-prepared UiO(Zr/Co)@CCNC/PAN exhibited superhydrophilic/underwater superoleophobic and anti-fouling properties. The membrane demonstrated excellent demulsification and gravity-driven separation capabilities for various oil-in-water emulsions, with superior permeation flux (1588–2557 L m−2 h−1) and separation efficiency (above 99 %). Furthermore, UiO (Zr/Co)@CCNC/PAN could activate peroxomonosulfate (PMS) under visible light to remove both high viscous crude oil-fouling and bio-fouling, exhibiting impressive photocatalytic self-cleaning and antibacterial activity. The generation of reactive radicals (O2−, OH and SO4−) and non-radical (1O2) species in UiO(Zr/Co)@CCNC/PAN+PMS system through multiple pathways was confirmed. Additionally, the band structure of UiO(Zr/Co) and synergistic photocatalytic-PMS activation mechanism were investigated. This work provides new insights into the design and fabrication of MOF modified superwetting nanofibrous membrane with inherent bonding, high permeation flux, anti-fouling and self-cleaning properties.
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