闫旭，李旭光，宋雯，等.铜锌铝水滑石制备及活化过氧单硫酸盐对水中土霉素降解性能［J］.中国粉体技术，2025，31（2）：59-70.

YAN Xu，LI Xuguang，SONG Wen，et al. Synthesis of CuZnAl layered double hydroxide and degradation of oxytetracycline in water by activated peroxymonosulfate［J］.China Powder Science and Technology，2025，31（2）：59-70.

收稿日期：2024-02-21，修回日期：2024-04-28，上线日期：2024-11-20。

摘要：【目的】利用水滑石（layered double hydroxide，LDH）粉体材料催化能力强、结构可调、制备难度低、分散性良好等优点及其在高级氧化技术中的应用潜能，研究铜锌铝水滑石（CuZnAl-LDH）的制备方法，以及活化过氧单硫酸盐 （peroxymonosulfate， PMS）降解水中难降解污染物的性能。【方法】采用共沉淀法制备并表征 CuZnAl-LDH-x；选择水中土霉素（oxytetracycline， OTC）进行降解实验，确定CuZnAl-LDH-x的较优制备条件，研究水化学条件对催化体系中OTC降解率的影响；探究 CuZnAl-LDH-x 活化PMS的催化机制和降解途径；在不同水体样本中进行催化体系的实际应用性能评估。【结果】制得的 CuZnAl-LDH-x 具有致密的六边形层状结构；当 Cu、Zn、Al 元素的物质的量比为 5∶1∶2 时，CuZnAl-LDH-1-PMS 体系对 OTC 降解效果最佳；在 CuZnAl-LDH-1-PMS 体系初始 pH 为 6、CuZnAl-LDH-1质量浓度为20mg/L、PMS浓度为 1.0mmol/L、OTC质量浓度为10mg/L时降解效果最佳，降解时间为 40 min时降解率高达 96. 25%； CuZnAl-LDH-1-PMS体系具有良好的抗干扰性， pH、无机阴离子和腐殖酸等因素的影响较小；在 CuZnAl-LDH-1-PMS体系降解 OTC过程中存在自由基和非自由基2种途径，其中羟基自由基对降解率的贡献最大；CuZnAl-LDH-1-PMS体系在4种实际水体中对 OTC 的降解率仍能达到 74%~95%。【结论】CuZnAl-LDH-x制备过程简便，具备高效活化PMS并降解抗生素类污染物的能力，可以作为基于过硫酸盐的高级氧化水处理技术的催化剂。

关键词： 铜锌铝水滑石；活化过氧单硫酸盐；土霉素；降解；高级氧化水处理技术

Objective Layered double hydroxide （LDH） is a widely available and cost-effective material known for its unique structure，large specific surface area，controllable interlayer ion exchange，and stability. LDH is capable of activating peroxymonosulfate （PMS）in advanced oxidation processes，offering advantages such as high efficiency，abundant surface hydroxyl groups，and a range of active species. In this study，CuZnAl-LDH was synthesized using the co-precipitation method. The structure and properties of CuZnAl-LDH were characterized using scanning electron microscopy （SEM），high-resolution transmission electron microscopy （HRTEM），X-ray diffraction （XRD），and Fourier-transform infrared（FTIR）spectroscopy. The synthesis of CuZnAl-LDH was explored leveraging the favorable attributes of LDHs，such as robust catalytic activity，customizable structure，simple synthesis process，excellent dispersibility，and potential application in advanced oxidation processes. Furthermore，the effectiveness of activated PMS in degrading recalcitrant pollutants in water was investigated，highlighting the potential of CuZnAl-LDH as a catalyst in advanced oxidation applications.

Methods The CuZnAl-LDH-x（x=1，2，…，5）was prepared by the co-precipitation method using CuCl₂·2H₂O，ZnCl₂ and AlCl₃·6H₂O at various molar ratios of Cu，Zn，and Al elements. The obtained powder was characterized by SEM，FTIR and XRD. The degradation experiments in CuZnAl-LDH-PMS system were conducted using OTC as a typical antibiotic in water. The experimental conditions，including the molar ratio of Cu，Zn，and Al elements，catalyst and PMS dosage，solution pH，and environmental factors such as inorganic anions and humic acid，were optimized. The mechanisms were also investigated by a quenching experiment and electron paramagnetic resonance（EPR） spectroscopy，and high performance liquid chromatography-mass spectrometry（ HPLC-MS） was used to determine the degradation products of OTC in CuZnAl-LDH-1-PMS system. With distilled water as a control，tap water，Yellow River water，a city landscape lake water ，and a campus landscape lake water were selected as water samples to conduct OTC degradation experiment .

Results and Discussion The synthesized CuZnAl-LDH exhibited a dense hexagonal layered structure with XRD peaks，typical LDH structure. Among the CuZnAl-LDH-x-PMS systems，the composition with a molar ratio of Cu，Zn，and Al elements at 5∶1∶2 demonstrated the highest efficiency in degrading OTC.Under optimized conditions（ initial pH of 6，CuZnAl-LDH-1 dosage of 20mg/L，and PMS concentration of 1mmol/L），the removal ratio of 10 mg/L OTC reached 96. 25% after 40 min. The CuZnAl-LDH-1-PMS catalytic system exhibited robust resistance to interference from environmental factors such as pH，inorganic anion and humic acid. The quenching experiment and EPR test showed that the degradation of OTC in CuZnAl-LDH-1- PMS system occurred via free radical pathway（·OH，SO₄⁻·，·O₂⁻） and non-free radical pathway（¹O₂），with·OH identified as the primary active radical species. A total of 10 intermediates were detected，leading to two degradation pathways for OTC. Compared with distilled water， the degradation rates of OTC in tap water， Yellow River water，a city landscape lake water，and a campus landscape lake water decreased slightly.

Conclusion CuZnAl-LDH-x was synthesized via a simple co-precipitation method and characterized by its typical layered structure，resembling hydrotalcite，and its properties. The CuZnAl-LDH-PMS system efficiently activates PMS to degrade OTC，achieving a maximum degradation rate. The CuZnAl-LDH-PMS catalytic system exhibited robust resistance to interference from factors like pH，inorganic anions（ Cl^-，HCO^3-，NO^3-，SO₄^2-），and humic acid（HA），with minimal impact on OTC degradation rates. Bursting and EPR experiments revealed that OTC degradation by the CuZnAl-LDH-PMS system involved both free radical pathways（·OH，SO₄⁻·，·O₂⁻） and non-free radical pathways（¹O₂）， with·OH identified as the primary active radical species. In actual water samples such as tap water，Yellow River water，a city and a campus landscape lake water，OTC degradation rates ranged from 74% to 95%，indicating the practical application potential of the CuZnAl-LDH-PMS catalytic system.

Keywords：CuZnAl layered double hydroxide；activated peroxymonosulfate；oxytetracycline；degradation；advanced oxidiation water treatment technology

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