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无机材料学报

• 研究论文 •    

MIL-53(Fe)衍生Fe3O4/HNTs/C复合材料活化单过硫酸盐降解四环素性能及机制研究

雷馨宇1,2, 吴丽梅1, 王晓龙3, 陈思全1, 牛蒙蒙1, 胡宸恺1, 王玮4, 唐宁1   

  1. 沈阳建筑大学 1.材料科学与工程;
    2.沈阳市高端陶瓷轴承重点实验室;
    3.机械工程学院, 沈阳 110168;
    4.众旺达(宁夏)技术咨询有限公司, 中卫 755000
  • 收稿日期:2026-03-02 修回日期:2026-05-25
  • 作者简介:雷馨宇(1995-), 女, 博士. E-mail: xinyulei@sjzu.edu.cn
  • 基金资助:
    国家自然科学基金(42202042); 辽宁省自然科学基金(2024-BSLH-250); 沈阳建筑大学沈阳市高端陶瓷轴承重点实验室(SJUKLHCB04)

MIL-53(Fe)-derived Fe3O4/HNTs/C Composite for Peroxymonosulfate Activation: Degradation Performance and Mechanism of Tetracycline

LEI Xinyu1,2, WU Limei1, WANG Xiaolong3, CHEN Siquan1, NIU Mengmeng1, HU Chenkai1, WANG Wei4, TANG Ning1   

  1. 1. School of Materials Science and Engineering, Shenyang Jianzhu University, Shenyang 110168, China;
    2. Key Laboratory of High-end Ceramic Bearing, Shenyang Jianzhu University, Shenyang 110168, China;
    3. School of Mechanical Engineering, Shenyang Jianzhu University, Shenyang 110168, China;
    4. Zhongwangda (Ningxia) Technical Consulting Co., Ltd., Zhongwei 755000, China
  • Received:2026-03-02 Revised:2026-05-25
  • About author:LEI Xinyu (1995-), female, PhD. E-mail: xinyulei@sjzu.edu.cn
  • Supported by:
    National Natural Science Foundation of China (42202042); Natural Science Foundation of Liaoning Province (2024-BSLH-250); Shenyang Jianzhu University, Key Laboratory of High-end Ceramic Bearing (SJUKLHCB04)

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摘要： Fe3O4因来源广泛、成本低廉常被用作过硫酸盐高级氧化技术的非均相催化剂, 但Fe3O4纳米颗粒易团聚的特性严重制约了其催化活性与稳定性。本研究以埃洛石纳米管(HNTs)为载体, 通过溶剂热法将MIL-53(Fe)前驱体原位生长于HNTs外表面, 经惰性气氛煅烧制得MIL-53(Fe)衍生Fe3O4/HNTs/C复合材料, 并系统探究了其活化单过硫酸盐(PMS)降解四环素(TC)的性能及机制。结果表明, Fe3O4/HNTs/C活化PMS对TC的降解效率达89.66%, 相较于Fe3O4/C和HNTs物理混合的降解效率提升了8.37%。Fe3O4/HNTs/C+PMS体系在pH 3~11范围内的降解效率均在82%以上, 在自来水和模拟海水中的降解效率均达到60%以上, 循环使用5次后降解效率仍在保持80%以上, 展现出优异的稳定性与可重复使用性。自由基捕获实验与电子顺磁共振测试证实, 体系中·SO4-、·OH、·O2-和1O2共同参与TC降解, 其中·O2-发挥主导作用。本研究还探索了反应过程中可能的中间产物以及TC降解路径。毒性评估显示中间产物的急性毒性、致突变性及发育毒性总体低于原始TC, 有效降低了环境风险。

关键词: 埃洛石, 四氧化三铁, 高级氧化, 单过硫酸盐, 四环素

Abstract: Fe3O4 is widely used as a heterogeneous catalyst in persulfate advanced oxidation technology due to its abundant availability and low cost. However, the inevitable agglomeration of nano-Fe3O4 severely restricts its catalytic activity and stability. In this study, halloysite nanotubes (HNTs) were employed as the carrier, and MIL-53(Fe) precursors were grown in-situ on the outer surface of HNTs via a solvothermal method, followed by calcination under an inert atmosphere to prepare MIL-53(Fe)-derived Fe3O4/HNTs/C composites. The performance and mechanism of Fe3O4/HNTs/C in activating peroxymonosulfate (PMS) for tetracycline (TC) degradation were systematically investigated. The results showed that the degradation efficiency of TC by Fe3O4/HNTs/C activating PMS reached 89.66%, which was 8.37% higher than that of the physically mixed sample of Fe3O4/C and HNTs. The Fe3O4/HNTs/C+PMS system maintained a TC degradation efficiency above 82% over a wide pH range of 3 to 11, and achieved a degradation efficiency of over 60% in both tap water and simulated seawater matrices. After 5 cycles, the degradation efficiency remained above 80%, demonstrating excellent stability and reusability. Free radical scavenging experiments and electron paramagnetic resonance tests confirmed that ·SO4-, ·OH, ·O2-, and 1O2 were involved in the degradation of TC, among which ·O2- played a dominant role. Furthermore, the possible intermediates and the potential degradation pathways of TC were explored. Toxicity evaluation indicated that the acute toxicity, mutagenicity, and developmental toxicity of the intermediates were generally lower than those of TC, effectively reducing the environmental risk.

Key words: halloysite, magnetite, advanced oxidation, peroxymonosulfate, tetracycline

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