Green deep eutectic solvents functionalized magnetic UiO-66-NH2: A novel strategy for improved stability and
Runan Chen1, Zhao Li1, Guohao Cheng1
1School of Environment, Henan Key Laboratory for Environmental Pollution Control, Key Laboratory for Yellow River and Huai River Water Environmental Pollution Control, Ministry of Education, Henan Normal University, Xinxiang, Henan, 453007, PR China.
Abstract:
The sustainable management of endocrine-disrupting pollutants such as bisphenol A (BPA) requires the development of efficient, reusable, and environmentally benign adsorbents. In this study, a green interfacial engineering strategy was proposed to enhance the stability and adsorption efficiency of magnetic metal-organic frameworks (MOFs) through deep eutectic solvents (DESs) functionalization. Magnetic UiO-66-NH2 (UiO-66-NH2@Fe3O4) was modified with a choline chloride-methacrylic acid DES to obtain a multifunctional composite (UiO-66-NH2@Fe3O4-DESs) featuring abundant hydrophilic and reactive carboxyl sites. The introduction of DES layers significantly improved the surface chemical environment and interfacial affinity of the MOFs without compromising magnetic separability. The optimized UiO-66-NH2@Fe3O4-DESs exhibited a maximum adsorption capacity of 129.28 mg g-1 toward BPA, which was nearly eight times higher than that of unmodified UiO-66-NH2@Fe3O4. Adsorption behavior followed the Freundlich isotherm and pseudo-second-order kinetic models, suggesting heterogeneous chemisorption controlled by surface-active sites. Thermodynamic analysis indicated negative ΔH0 (-9.32 to -19.94 kJ mol-1) and ΔS0 (-48 to -52 J mol-1 K-1), confirming an exothermic and spontaneous process accompanied by decreased interfacial entropy due to ordered BPA alignment. The composite maintained stable adsorption under varying temperature, pH, and ionic strength, and retained 93.09% of its capacity after five regeneration cycles. Furthermore, high recoveries (89.55-117.19%) and low RSDs (<5.10%) were achieved in real environmental samples, demonstrating its reliability in complex matrices. This study presents a sustainable and scalable strategy for designing DES-functionalized MOFs offering practical potential for advanced water purification and environmental management.
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