Loosely Sandwich-Structured Membranes Decorated with UiO-66-NH2 for Efficient Antibiotic Separation and Organic Solvent Resistance

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-1 UiO-66-NH2), 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 N,N-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.