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用于高效去除六价铬及阴离子/阳离子染料的壳聚糖/碳/ZnMn₂O₄纳米复合材料

Chitosan/carbon/ZnMn₂O₄ nanocomposite for efficient removal of chromium(VI) and anionic/cationic dyes.

作者信息

Mohamed Amna, Galhoum Ahmed A, Saad A, Wageh S

机构信息

Department of Mathematics, College of Science and Humanity Studies in Alkharj, Prince Sattam bin Abdulaziz University.

Nuclear Materials Authority, P.O. Box 530, El-Maadi, Cairo, Egypt.

出版信息

Int J Biol Macromol. 2025 Sep;321(Pt 4):146329. doi: 10.1016/j.ijbiomac.2025.146329. Epub 2025 Jul 30.

Abstract

This work advances waste-to-resource circularity by transforming battery waste into an efficient sorbent, addressing mixed-pollutant challenges in industrial wastewater. An innovative mesoporous ternary chitosan/carbon/ZnMn₂O₄ nanocomposite (Cs/C/ZMO) was engineered through a two-step synthesis process for the removal of both anionic and cationic pollutants. First, zinc‑carbon battery waste was hydrothermally converted in ZnSO₄ solution to carbon/ZnMn₂O₄ (C/ZMO), followed by chitosan integration (1:2 wt/wt, respectively) via alkaline co-precipitation and epichlorohydrin crosslinking. Structural characterization (SEM, BET, XRD, EDX, CHN/O, XPS, and pHzpc) confirmed morphology, mesoporosity, ZnMn₂O₄ spinel phase, elemental composition, surface functionality, and charge. Sorption capacities were exceptional: Cr(VI) reached ∼6.565 mmol/g (pH 2.5, 328 K), while methyl orange (MO) and methylene blue (MB) achieved ∼0.621 mmol/g (pH 2.5) and ∼ 0.790 mmol/g (pH 6.0), respectively, at 298 K. Equilibrium was attained within 50-75 min, following pseudo-first-order kinetics. Cr(VI) removal proceeded via synergistic sorption, coordination, and electro-redox mechanisms. Thermodynamically, Cr(VI) sorption was endothermic (reciprocal to MO/MB), entropy-driven, and a spontaneous process. Reusability tests demonstrated good stability and durability, retaining ∼88 % capacity over eight cycles with >90 % desorption efficiency. In acidic tannery effluent (pH 2.5), Cs/C/ZMO sorbent exhibited exceptional selectivity for Cr(VI) removal over competing cations, underscoring its practical utility.

摘要

这项工作通过将电池废料转化为高效吸附剂,推动了从废物到资源的循环利用,解决了工业废水中的混合污染物挑战。通过两步合成工艺设计了一种创新的介孔三元壳聚糖/碳/ZnMn₂O₄纳米复合材料(Cs/C/ZMO),用于去除阴离子和阳离子污染物。首先,将锌碳电池废料在ZnSO₄溶液中进行水热转化为碳/ZnMn₂O₄(C/ZMO),然后通过碱性共沉淀和环氧氯丙烷交联将壳聚糖整合(分别为1:2重量/重量)。结构表征(SEM、BET、XRD、EDX、CHN/O、XPS和pHzpc)证实了形态、介孔性、ZnMn₂O₄尖晶石相、元素组成、表面官能团和电荷。吸附容量非常出色:在298K时,Cr(VI)达到约6.565 mmol/g(pH 2.5,328K),而甲基橙(MO)和亚甲基蓝(MB)分别达到约0.621 mmol/g(pH 2.5)和约0.790 mmol/g(pH 6.0)。遵循准一级动力学,在50 - 75分钟内达到平衡。Cr(VI)的去除通过协同吸附、配位和电氧化还原机制进行。从热力学角度看,Cr(VI)的吸附是吸热的(与MO/MB相反),由熵驱动,是一个自发过程。可重复使用性测试表明具有良好的稳定性和耐久性,在八个循环中保持约88%的容量,解吸效率>90%。在酸性制革废水(pH 2.5)中,Cs/C/ZMO吸附剂对Cr(VI)的去除表现出优于竞争性阳离子的卓越选择性,突出了其实际应用价值。

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