乙炔黑/Fe3O4阴极制备及电Fenton氧化降解2,4,6-三氯苯酚

doi:10.16085/j.issn.1000-6613.2024-0042

摘要/Abstract

摘要：

以泡沫镍为载体，采用乙炔黑粉末和纳米Fe₃O₄为催化剂，通过涂抹/压实/煅烧方式制备一种能够实现原位产生H₂O₂并在Fe(Ⅱ)存在条件下活化H₂O₂生成羟基自由基（·OH）的阴极材料。通过X射线衍射（XRD）、扫描电子显微镜（SEM）对样品的晶格结构、形貌结构等进行表征；将制备所得阴极材料应用于电芬顿系统处理2,4,6-三氯苯酚模拟废水，探究乙炔黑/Fe₃O₄材料的电催化性能。结果表明，电芬顿体系中，Fe₃O₄/C为3∶7、电流强度50mA、初始pH为3的最佳实验条件下，电解120min时2,4,6-三氯苯酚的去除率为70.8%，且乙炔黑/Fe₃O₄电极有效拓宽了电芬顿系统的pH适用范围（3~11）。Fe₃O₄以多面体结构形式镶嵌在乙炔黑表面，为H₂O₂的原位产生和活化奠定了物质基础。

关键词: 电化学, 催化, 自由基, 四氧化三铁, 乙炔黑, 2,4,6-三氯苯酚

Abstract:

A cathode material was prepared by coating, compaction and calcination using nickel foam as a carrier, acetylene black powder, and nano Fe₃O₄ as a catalyst. This material is capable of achieving in-situ generation of H₂O₂ and activation of H₂O₂ to generate hydroxyl radicals (·OH) in the presence of Fe(Ⅱ). X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to characterise the lattice and morphological structures of the samples. The cathode materials prepared were applied to the electro-Fenton system to treat simulated wastewater containing 2,4,6-trichlorophenol, and the electrocatalytic performance of acetylene black/Fe₃O₄ materials was investigated. Under the optimal experimental conditions of a Fe₃O₄/C ratio of 3∶7, a current intensity of 50mA and an initial pH of 3 in the electro-Fenton system, the removal rate of 2,4,6-trichlorophenol was 70.8% after 120min of electrolysis. The acetylene black/Fe₃O₄ electrodes effectively broadened the pH range (3—11) of the electro-Fenton system. The polyhedral structure of Fe₃O₄ was embedded in the surface of acetylene black, providing a material foundation for the in-situ generation and activation of H₂O₂.

Key words: electrochemistry, catalysis, radical, Fe₃O₄, acetylene black, 2,4,6-TCP

中图分类号:

X703.1

何然, 梁宏, 黄洪, 羊宥郦, 郑强, 李琋. 乙炔黑/Fe₃O₄阴极制备及电Fenton氧化降解2,4,6-三氯苯酚[J]. 化工进展, 2025, 44(1): 572-582.

HE Ran, LIANG Hong, HUANG Hong, YANG Youli, ZHENG Qiang, LI Xi. Preparation of acetylene black/Fe₃O₄ catalysed cathodic electrode and removal of 2,4,6-trichlorophenol by electro-Fenton oxidation[J]. Chemical Industry and Engineering Progress, 2025, 44(1): 572-582.

图/表 16

图1 电-Fenton反应体系装置1—磁力搅拌器；2—电解池；3—磁力搅拌转子；4—Pt片阳极（1cm×2cm×0.5mm）；5—乙炔黑/Fe3O4电极（2cm×2cm×0.5mm）；6—电源

图2 纯Fe3O4和乙炔黑/Fe3O4阴极材料的XRD谱图

图3 改性前后阴极材料的SEM图

图4 乙炔黑/Fe3O4/泡沫镍的XPS谱图

图5 泡沫镍和乙炔黑/Fe3O4/泡沫镍电极的循环伏安曲线

图6 Fe3O4/C比对2,4,6-TCP去除率的影响

图7 电流对2,4,6-TCP降解效率及TOC的影响

图8 初始pH对2,4,6-TCP去除率的影响

图9 乙炔黑/Fe3O4电极的循环次数对降解效果的影响

图10 反应体系中铁溶出随时间的变化

图11 不同Fe3O4/C对·OH及H2O2产生量的影响

表1 Fe3O4/乙炔黑质量比对Fe(Ⅱ)、H2O2浓度的影响

Fe₃O₄/C	Fe(Ⅱ)摩尔浓度 /mmol·L^-1	H₂O₂摩尔浓度 /mmol·L^-1	摩尔比
1∶9	0.12	0.68	1∶6
3∶7	0.37	0.28	5∶4
5∶5	0.61	0.17	10∶3
7∶3	0.87	0.04	20∶1
9∶1	1.12	0.02	55∶1

图12 阳极氧化的影响

图13 2,4,6-TCP去除率随电解时间的变化趋势

图14 2,4,6-TCP模拟废水的GC-MS色谱图及中间产物局部放大图

图15 电芬顿体系中2,4,6-TCP降解路径

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乙炔黑/Fe₃O₄阴极制备及电Fenton氧化降解2,4,6-三氯苯酚

Preparation of acetylene black/Fe₃O₄ catalysed cathodic electrode and removal of 2,4,6-trichlorophenol by electro-Fenton oxidation

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