自支撑阴极电Fenton降解氧氟沙星性能与机制研究

doi:10.19965/j.cnki.iwt.2025-0059

摘要/Abstract

摘要：

高效稳定自支撑阴极材料是电Fenton技术在水处理领域应用的关键。采用酸处理-黏结-焙烧法制备氧掺杂炭黑修饰碳毡（O-CB/CF）自支撑碳阴极。扫描电子显微镜、X射线衍射和X射线光电子能谱等技术表明O-CB成功负载到碳毡表面并且在碳毡表面均匀分布。氧掺杂显著提高了炭黑材料的电子转移性能和两电子氧还原选择性，通过促进过氧化氢（H₂O₂）电合成强化其电Fenton降解污染物性能。以O-CB/CF作为阴极，在最佳反应条件下〔电压为0.2 V vs. RHE，pH为5，氧氟沙星（OFL）初始质量浓度为20 mg/L，Fe²⁺质量浓度为20 mg/L〕，反应10 min废水中的OFL去除率可接近100%，反应120 min后总有机碳去除率可达48.5%，为CB/CF阴极体系下的2.5倍。自由基捕获实验和电子顺磁光谱结果表明·OH是该体系中的主要活性物种。连续20次降解实验OFL的去除率均接近100%，证明制备的O-CB/CF自支撑碳阴极具有较好的稳定性。

关键词: 氧掺杂炭黑, 电Fenton, 改性碳毡, 氧氟沙星

Abstract:

Highly efficient and stable self-supporting cathode material are key to the application of Electro-Fenton technology in practical wastewater treatment. In this study, acid treatment-binding-roasting method was utilized to prepare an oxygen-doped carbon black modified carbon felt(O-CB/CF) self-supporting electrode. The structure of the electrode material was characterized using scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy, confirming the successful loading of O-CB on the cathode surface. Oxygen doping significantly enhanced the electron transfer properties and the two-electron oxygen reduction capability of CB, thus facilitating the electrosynthesis of H₂O₂ and boosting electro-Fenton performance toward pollutants degradation. Under the optimal conditions (applied potential of 0.2 V vs. RHE, pH=5, initial ofloxacin(OFL) concentration of 20 mg/L, Fe²⁺ concentration of 20 mg/L), the O-CB/CF-based EF system could completely degrade OFL within 10 min, achieving a total organic carbon(TOC) removal rate of 48.5% within 120 min, which was 2.5 times higher than that of CB/CF. The radical capture experiments and electron paramagnetic spectra showed that ·OH was the main active species in this system. The good stability of O-CB/CF was proved by 20 consecutive OFL degradation experiments with removal efficiency of 100%.

Key words: oxygen-doped carbon black, electro-Fenton, modified carbon felt, ofloxacin

中图分类号:

X703.1

李洪祥, 程硕, 齐叶惠, 李鸿莉, 赵坤, 牛军峰. 自支撑阴极电Fenton降解氧氟沙星性能与机制研究[J]. 工业水处理, 2025, 45(12): 47-54.

Hongxiang LI, Shuo CHENG, Yehui QI, Hongli LI, Kun ZHAO, Junfeng NIU. Mechanism of self-supporting cathode for degradation of ofloxacin by electro-Fenton process[J]. Industrial Water Treatment, 2025, 45(12): 47-54.

https://www.iwt.cn/CN/Y2025/V45/I12/47

图/表 12

图1 CB、O-CB、CF、O-CB/CF的SEM （a）CB；（b）O-CB；（c）放大300倍的CF；（d）放大5 000倍的CF；（e）放大300倍的O-CB/CF；（f）放大5 000倍的O-CB/CF。

Fig.1 SEM images of CB，O-CB，CF， and O-CB/CF

图2 CB、O-CB、CF以及O-CB/CF的X射线衍射谱图

Fig.2 XRD spectra of CB， O-CB， CF， and O-CB/CF

图3 CB、O-CB、CF以及O-CB/CF的X射线光电子能谱全扫谱图

Fig.3 Full scan XPS spectra of CB， O-CB， CF， and O-CB/CF

图4 CB、O-CB的O 1s反卷积谱图

Fig.4 O 1s deconvolution spectra of CB and O-CB

图5 CB以及O-CB催化剂在Ar（虚线）和O₂（实线）氛围下的CV曲线

Fig.5 CV curves of CB and O-CB catalysts in Ar （dashed lines） and O₂ （solid lines） atmospheres

图6 CB和O-CB的EIS谱图

Fig.6 EIS spectra of CB and O-CB

图7 CB和O-CB的旋转环盘电极测试

Fig.7 RRDE tests of CB and O-CB

图8 O-CB/CF、CB/CF以及CF上的H₂O₂累积量

Fig.8 H₂O₂ accumulation on O-CB/CF， CB/CF and CF

图9 不同电极材料降解OFL的性能

Fig.9 Performance of OFL degradation using different electrode materials

图10 操作参数对OFL降解效果影响及对应的动力学常数

Fig.10 Effects of operating parameters on OFL degradation efficiency and corresponding kinetic constants

图11 不同猝灭剂对OFL降解的抑制效果

Fig.11 Inhibition effect of different quenchers on OFL degradation

图12 未施加电位与施加电压条件下DMPO-∙OH加合物的EPR

Fig.12 EPR spectra of DMPO-∙OH adducts with/without applied potential

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