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UiO-66-NH 修饰的疏松三明治结构膜用于高效抗生素分离和有机溶剂抗性。

Loosely Sandwich-Structured Membranes Decorated with UiO-66-NH for Efficient Antibiotic Separation and Organic Solvent Resistance.

机构信息

Key Laboratory of Environmental Biology and Pollution Control, College of Environmental Science and Engineering, Hunan University, Changsha 410082, China.

State Environmental Protection Key Laboratory of Monitoring for Heavy Metal Pollutants, Changsha 410019, China.

出版信息

ACS Appl Mater Interfaces. 2022 Aug 31;14(34):38990-39003. doi: 10.1021/acsami.2c12146. Epub 2022 Aug 17.

Abstract

Thin-film nanocomposite (TFN) membranes with efficient molecular separation and organic solvent resistance are active in demand in wastewater treatment and resource reclamation, meeting the goal of emission peaks and carbon neutrality. In this work, a simple and rational design strategy has been employed to construct a sandwich-structured membrane for removing fluoroquinolone antibiotics and recycling organic solvents. The sandwich-structured membrane is composed of a porous substrate, a hydrophilic tannic acid-polyethyleneimine (TA-PEI) interlayer, and a polyamide (PA) selective layer decorated with metal-organic framework (PA-MOF). Results manifest that the hydrophilic TA-PEI interlayer played a bridging and gutter effect to achieve effective control in amide storage, amine diffusion, and nanomaterial downward leakage at the immiscible interface. The PA-MOF selective layer has been changed to a loosely crumpled surface, endowing functionalities on the sandwich-structured membrane that included limited pores, strengthened electronegativity, and stronger hydrophilicity. Thus, an enhanced water flux of 87.23 ± 7.43 LMH was achieved by the TFN-2 membrane (0.04 mg·mL UiO-66-NH), which is more than five times that of the thin-film composite membrane (17.46 ± 3.88 LMH). The rejection against norfloxacin, ciprofloxacin, and levofloxacin is 92.94 ± 1.60%, 94.62 ± 1.29%, and 96.92 ± 1.05%, respectively, effectively breaking through the "trade-off" effect between membrane permeability and rejection efficiency. Further antifouling results showed that the sandwich-structured membrane had lower flux decay ratios (3.36∼7.07%) and higher flux recovery ratios (93.40∼98.40%), as well as superior long-term stability after 30 days of filtration. Moreover, organic solvent resistance testing confirms that the sandwich-structured membrane maintained stable solvent flux and better recovery rates in ethanol, acetone, isopropanol, and ,-dimethylformamide. Detailed nanofiltration mechanism studies revealed that these outstanding performances are based on the joint effect of the TA-PEI interlayer and PA-MOF selective layer, proposing a new perspective to break through the bottleneck of nanofiltration application in a complex environment.

摘要

具有高效分子分离和有机溶剂抗性的薄膜纳米复合(TFN)膜在废水处理和资源回收中需求量很大,符合减排和碳中和的目标。在这项工作中,采用了一种简单而合理的设计策略,构建了一种用于去除氟喹诺酮类抗生素和回收有机溶剂的三明治结构膜。三明治结构膜由多孔基底、亲水性单宁酸-聚乙烯亚胺(TA-PEI)夹层和负载金属-有机骨架(PA-MOF)的聚酰胺(PA)选择性层组成。结果表明,亲水性 TA-PEI 夹层起到了桥接和沟渠的作用,在不混溶界面实现了酰胺储存、胺扩散和纳米材料向下泄漏的有效控制。PA-MOF 选择性层变成了松散皱缩的表面,赋予三明治结构膜有限的孔、增强的电负性和更强的亲水性等功能。因此,TFN-2 膜(负载 0.04mg·mL UiO-66-NH 的膜)的水通量提高到 87.23±7.43LMH,是薄膜复合膜(17.46±3.88LMH)的五倍多。对诺氟沙星、环丙沙星和左氧氟沙星的截留率分别为 92.94±1.60%、94.62±1.29%和 96.92±1.05%,有效地突破了膜渗透性和截留效率之间的“权衡”效应。进一步的抗污染结果表明,三明治结构膜具有较低的通量衰减率(3.36∼7.07%)和较高的通量恢复率(93.40∼98.40%),以及在过滤 30 天后具有更好的长期稳定性。此外,有机溶剂阻力测试证实,三明治结构膜在乙醇、丙酮、异丙醇和 N,N-二甲基甲酰胺中保持稳定的溶剂通量和更好的回收率。详细的纳滤机制研究表明,这些优异的性能是 TA-PEI 夹层和 PA-MOF 选择性层共同作用的结果,为突破纳滤在复杂环境中的应用瓶颈提供了新的视角。

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