Chen Zhaoxia, Xue Jinjuan, Zhang Jiaqian, Qu Jianan, Huang Kaiwen, Wang Mingxin
School of Environmental Science and Engineering, Changzhou University, Changzhou 213164, PR China.
School of Environmental Science and Engineering, Changzhou University, Changzhou 213164, PR China; Jiangsu Petrochemical Safety and Environmental Protection Engineering Research Center, Changzhou 213164, PR China.
Int J Biol Macromol. 2024 Dec;282(Pt 4):137158. doi: 10.1016/j.ijbiomac.2024.137158. Epub 2024 Nov 2.
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-NH (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 h) 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 (O, OH and SO) and non-radical (O) 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.
超润湿性膜的开发是分离乳化含油废水的一种很有前景的方法。然而，诸如无外压时通量低和膜污染等挑战阻碍了膜的性能。在此，我们通过EDC/NHS反应经由化学键将共掺杂Zr的UiO-66-NH（UiO(Zr/Co)）纳米颗粒接枝到羧基化纤维素纳米晶体（CCNC）-聚丙烯腈（PAN）混合基质静电纺丝膜上，制备了一种新型纳米纤维膜。CCNC起到了双重作用，既增强了膜的亲水性，又为UiO(Zr/Co)提供了连接点。所制备的UiO(Zr/Co)@CCNC/PAN表现出超亲水/水下超疏油和抗污染性能。该膜对各种水包油乳液表现出优异的破乳和重力驱动分离能力，具有优异的渗透通量（1588 - 2557 L m⁻² h⁻¹）和分离效率（高于99%）。此外，UiO(Zr/Co)@CCNC/PAN在可见光下可活化过氧单硫酸盐（PMS）以去除高粘性原油污垢和生物污垢，表现出令人印象深刻的光催化自清洁和抗菌活性。证实了UiO(Zr/Co)@CCNC/PAN + PMS体系中通过多种途径产生活性自由基（O₂⁻、OH和SO₄⁻）和非自由基（¹O₂）物种。此外，还研究了UiO(Zr/Co)的能带结构和协同光催化 - PMS活化机制。这项工作为具有固有键合、高渗透通量、抗污染和自清洁性能的MOF改性超润湿性纳米纤维膜的设计和制备提供了新的见解。
