钙掺杂氯氧化铋类Fenton体系去除土霉素的作用机制

doi:10.19965/j.cnki.iwt.2024-0625

摘要/Abstract

摘要：

为克服金属活性位点的氧化还原反应限制，提高H₂O₂利用率，实现水中土霉素的高效去除，采用水热法制备了钙掺杂的BiOCl（Ca-BiOCl）催化剂，通过X射线衍射技术、透射电子显微镜、拉曼光谱、X射线光电子能谱等表征技术对样品的形貌和结构进行表征分析。研究了Ca-BiOCl催化类Fenton降解土霉素的性能，考察了相关反应参数和环境条件对土霉素降解效果的影响。结果表明：Ca的最佳掺杂量为1.2 mmol/L，此时12Ca-BiOCl的催化活性最佳。在12Ca-BiOCl催化的类Fenton体系中，当H₂O₂投加量为2 mmol/L，12Ca-BiOCl投加量为0.5 g/L时，土霉素在45 min内的去除率可达80.3%，该体系中的主要活性物种为超氧自由基（O₂ ^·-）和单线态氧（¹O₂）。此外，在pH=3或氯离子条件下，土霉素的去除率有所下降，在pH为5~9的范围内或在硝酸根离子和腐殖酸条件下，土霉素的去除率几乎没有变化，表明所制备的12Ca-BiOCl具有较好的环境适用性。

关键词: 钙掺杂BiOCl, 类Fenton, 土霉素

Abstract:

To overcome the limitations of redox reactions at metal active sites, enhance the utilization of H₂O₂, and achieve efficient removal of oxytetracycline in water, calcium-doped BiOCl(Ca-BiOCl) catalysts were prepared using a hydrothermal method. The morphology and structure of the samples were characterized by X-ray diffraction technique, transmission electron microscopy, Raman spectrum, X-ray photoelectron spectroscopy, and other techniques. The performance of Ca-BiOCl in catalyzing Fenton-like removal of oxytetracycline was investigated, and the effects of relevant reaction parameters and environmental conditions on oxytetracycline degradation were examined. The experimental results showed that the optimal Ca doping amount was 1.2 mmol/L, with 12Ca-BiOCl exhibiting the best catalytic activity. In the Fenton-like system catalyzed by 12Ca-BiOCl, with H₂O₂ dosage of 2 mmol/L and 12Ca-BiOCl concentration of 0.5 g/L, the removal rate of oxytetracycline reached 80.3% within 45 minutes. The main active species in this system were superoxide radicals(O₂ ^·-) and singlet oxygen(¹O₂). Additionally, the removal rate of oxytetracycline decreased under pH=3 or in the presence of chloride ions, while the removal rate showed almost no change within the pH range of 5-9 or in the presence of nitrate ions and humic acid, indicating that the prepared 12Ca-BiOCl had good environmental adaptability.

Key words: calcium-doped BiOCl, Fenton-like, oxytetracycline

中图分类号:

X703.1

周大为, 胡偲倢, 谭艳忠, 冯云海, 赖萃, 晏铭. 钙掺杂氯氧化铋类Fenton体系去除土霉素的作用机制[J]. 工业水处理, 2025, 45(8): 76-82.

Dawei ZHOU, Sijie HU, Yanzhong TAN, Yunhai FENG, Cui LAI, Ming YAN. Mechanism of oxytetracycline removal by Fenton-like system catalyzed by calcium-doped BiOCl[J]. Industrial Water Treatment, 2025, 45(8): 76-82.

https://www.iwt.cn/CN/Y2025/V45/I8/76

图/表 12

图1 BiOCl、9Ca-BiOCl、12Ca-BiOCl、15Ca-BiOCl的XRD

Fig.1 XRD patterns of BiOCl，9Ca-BiOCl，12Ca-BiOCl，and 15Ca-BiOCl

图2 12Ca-BiOCl的TEM（a）、HRTEM（b）、SAED（c）和能谱图（d）

Fig.2 TEM（a），HRTEM（b），SAED（c），and EDS mapping images（d） of 12Ca-BiOCl

图3 12Ca-BiOCl和BiOCl的拉曼光谱图

Fig.3 Raman spectra of 12Ca-BiOCl and BiOCl

图4 12Ca-BiOCl和BiOCl的Bi 4f高分辨率图

Fig.4 High-resolution image of Bi 4f of 12Ca-BiOCl and BiOCl

图5 不同催化体系下OTC的降解效率

Fig.5 Degradation efficiency of OTC in different catalytic systems

图6 12Ca-BiOCl投加量对OTC降解效果的影响

Fig.6 Effects of 12Ca-BiOCl dosage on the degradation of OTC

图7 H₂O₂浓度对OTC降解的影响

Fig.7 Effects of H₂O₂ concentration on the degradation of OTC

图8 初始溶液pH对OTC降解的影响

Fig.8 Effects of initial solution pH on the degradation of OTC

图9 不同阴离子和HA对OTC降解的影响

Fig.9 Effects of different anions and humic acid on the degradation of OTC

图10 类Fenton体系的掩蔽试验

Fig.10 Masking experiments of Fenton-like system

图11 类Fenton体系的 EPR图

Fig.11 EPR images of Fenton-like system

图12 12Ca-BiOCl活化H₂O₂降解OTC的循环降解试验

Fig.12 Cyclical performance of 12Ca-BiOCl to activate H₂O₂for OTC degradation

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