The CoFe2O4/CeO2 composite material activates PMS to degrade tetracycline hydrochloride

doi:10.11949/0438-1157.20250672

Abstract

Abstract:

Water pollution caused by the diffusion of tetracycline hydrochloride (TC-HCl) has seriously endangered human beings and the environment. CoFe₂O₄/CeO₂ composites with different CeO₂ contents were prepared by the sol-gel-combustion method. And it was used as an activator of peroxymonosulfate (PMS) to promote the degradation rate of tetracycline (TC-HCl). The results show that the degradation rate of 10 mg/L TC-HCl can reach 91.94% within 40 min, and it has a good removal effect on TC-HCl within a wide pH range (3—9). Active species capture experiments, electron paramagnetic resonance spectroscopy, and high-valent metal probe analysis confirmed the presence of free radicals ( $S O 4 - ·$ and ·OH) and non-radicals (¹O₂ and high-valent metal oxygen species) in the catalytic degradation of TC-HCl. The degradation intermediates were analyzed by liquid chromatography-mass spectrometry. Combined with the XPS before and after the CoFe₂O₄/CeO₂ reaction, the degradation pathway and reaction mechanism of TC-HCl were proposed. Through cyclic experiments, inorganic anion interference experiments and degradation experiments on other pollutants, it is demonstrated that CoFe₂O₄/CeO₂ has good stability and practicability. This work aims to improve the performance of PMS activated spinel-type ferrite materials and provide a reference for solving the treatment of antibiotics in the real environment.

Key words: tetracycline hydrochloride, peroxymonosulfate, degradation, activation, CoFe₂O₄, CeO₂

摘要：

由盐酸四环素（TC-HCl）扩散引起的水体污染已严重危害人类健康和环境。采用溶胶-凝胶-燃烧法制备了不同CeO₂含量的CoFe₂O₄/CeO₂复合材料，并将其作为过氧单硫酸盐（PMS）活化剂促进四环素（TC-HCl）的降解。结果表明，在CoFe₂O₄/CeO₂/PMS体系中，对10 mg/L的TC-HCl在40 min内降解率可达91.94%，同时在较宽的pH（3~9）区间内对TC-HCl有较好的去除效果。利用活性物种捕捉实验、电子顺磁共振波谱和高价金属探针分析确定了自由基（ $S O 4 - ·$ 和·OH）和非自由基（¹O₂和高价金属氧物种）存在于TC-HCl的催化降解中。利用液相色谱-质谱联用技术对降解中间体进行分析，并结合CoFe₂O₄/CeO₂反应前后的XPS分析提出了TC-HCl的降解途径和反应机理。通过循环实验、无机阴离子干扰实验以及对其他污染物的降解实验，说明CoFe₂O₄/CeO₂具有较好的稳定性和实用性。本工作为提高尖晶石型铁氧体材料活化PMS的性能，解决现实环境中抗生素的降解问题提供了参考。

关键词: 盐酸四环素, 过氧单硫酸盐, 降解, 活化, CoFe₂O₄, CeO₂

CLC Number:

TQ 028.8

Tian YANG, Huixia GUO, Mengci SUN. The CoFe₂O₄/CeO₂ composite material activates PMS to degrade tetracycline hydrochloride[J]. CIESC Journal, 2025, 76(12): 6680-6695.

杨田, 郭惠霞, 孙梦慈. CoFe₂O₄/CeO₂复合材料活化PMS降解盐酸四环素[J]. 化工学报, 2025, 76(12): 6680-6695.

Figures/Tables 15

Fig.1 Preparation process of CoFe2O4/CeO2

Fig.2 XRD patterns of the prepared samples (a,b); N2 adsorption-desorption isotherm (c) and aperture distribution map(d) of CoFe2O4, CeO2 and CoFe2O4/0.30CeO2

Table 1 Specific surface area， pore volume and average pore diameter of CoFe2O4， CeO2 and CoFe2O4/0.3CeO2

样品	比表面积/(m²/g)	孔体积/(cm³/g)	平均孔径/nm
CoFe₂O₄	3.25±0.02	0.06	62.78
CeO₂	8.99±0.02	0.20	61.23
CoFe₂O₄/0.3CeO₂	34.58±0.02	0.15	18.86

Fig.3 SEM of CoFe2O4 (a), CeO2 (b), CoFe2O4/0.30CeO2 (c); TEM (d), HRTEM (e), SAED (f) and EDS (g) of CoFe2O4/0.30CeO2

Fig.4 Influence of different systems on TC-HCl (a); The effect of different CeO2 complex amount on TC-HCl degradation efficiency (c); (a), (c) Corresponding pseudo-first-order kinetic model [(b),(d)] (experimental conditions: Ccat=0.25 g/L, CPMS=0.30 mmol/L, CTC-HCl=10 mg/L, T=303 K)

Fig.5 The influence of catalyst addition amount (a), PMS addition amount (b), and initial pH (c) on catalytic performance; (d)—(f) The pseudo-first-order kinetic model of the catalyst corresponding to (a—c)(experimental conditions: Ccat=0.25 g/L, CPMS=0.30 mmol/L, CTC-HCl=10 mg/L, T=303 K)

Table 2 Summarized the results of similar work

催化剂	工作内容	文献
ZrO₂ / MnFe₂O₄	ZrO₂/ MnFe₂O₄ -10 = 0.20 g/L，PDS = 6.0 mmol/L，pH = 7.1，TC=20 mg/L，120 min后TC降解效率达到85.2％	[19]
CoFe₂O₄/高岭石	CFO/K-40%= 0.50 g/L，H₂O₂ = 1.0 ml，pH = 4，TC=30 mg/L，30 min内降解效率可达84.82%	[20]
CoFe₂O₄/氮化碳	CFO/CN = 0.5 g/L，PMS = 1.0 mmol/L，TC=44.4 mg/L，10 min后TC降解效率达到86％	[21]
CoFe₂O₄@MoS₂	CoFe₂O₄/MoS₂ = 0.20 g/L，PDS =0.5 mmol/L，pH = 7，TC=10 mg/L，30 min后TC降解效率达到93％	[22]
CoFe₂O₄/二氧化硅	CFO/MCM-41 = 0.20 g/L，PDS =0.15 mmol/L，pH = 7，SMX=10 mg/L，30 min后TC降解效率达到90.39％	[23]
CoFe₂O₄/CeO₂	CoFe₂O₄/CeO₂ = 0.25 g/L，PMS =0.15 mmol/L，TC-HCl=10 mg/L，40 min后TC-HCl降解效率达到91.94％	本文

Fig.6 Effects of different concentrations of inorganic anions on TC-HCl degradation(Experimental conditions: Ccat=0.25 g/L, CPMS=0.30 mmol/L, CTC-HCl=10 mg/L, T=303 K)

Fig.7 Effects of different concentrations of scavengers on the removal of TC-HCl in CoFe2O4/0.30CeO2/PMS system(a)—(d); EPR spectra captured by DMPO showed SO4-·, ·OH(e); (f) TEMP captures EPR spectrum (Experimental conditions：Ccat=0.25 g/L, CPMS=0.30 mmol/L, CTC-HCl=10 mg/L, T=303 K)

Fig.8 XPS spectra of CoFe2O4/0.30CeO2 before and after the reaction

Fig.9 The i-t curve(a); OCP curve(b) of CoFe2O4/0.30CeO2/PMS system LC-MS chromatogram of the degradation of PMSO to generate PMSO2(c); The secondary mass spectra of PMSO and PMSO2 (d); The curves of the degradation of PMSO and the generation of PMSO2 (e)(Experimental conditions:Ccat=0.25 g/L, CPMS=0.30 mmol/L, CTC-HCl=10 mg/L, T=303 K)

Fig.10 Degradation mechanism of TC-HCl

Fig.11 Total ion flow diagram of samples at different time periods during the degradation of TC-HCl

Fig.12 Possible pathways for TC-HCl degradation by CoFe2O4/0.30CeO2

Fig.13 Degradability of other pollutants(a); Cyclic experiment (b); Before and after the use of XRD (c) (Experimental conditions: Ccat=0.25 g/L, CPMS=0.30 mmol/L, CTC-HCl=10 mg/L, T=303 K)

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The CoFe₂O₄/CeO₂ composite material activates PMS to degrade tetracycline hydrochloride

CoFe₂O₄/CeO₂复合材料活化PMS降解盐酸四环素

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