宽pH条件下Mn3O4/ACF复合阴极类电芬顿体系降解亚甲基蓝

doi:10.11949/j.issn.0438-1157.20160775

化工学报 ›› 2017, Vol. 68 ›› Issue (1): 305-312.DOI: 10.11949/j.issn.0438-1157.20160775

宽pH条件下Mn₃O₄/ACF复合阴极类电芬顿体系降解亚甲基蓝

何盈盈, 孟建, 马亚利, 张潇予

西安建筑科技大学理学院, 陕西西安 710055

收稿日期:2016-06-06 修回日期:2016-09-29 出版日期:2017-01-05 发布日期:2017-01-05
通讯作者: 何盈盈
基金资助:
国家自然科学基金项目（51378414）；陕西省自然科学基础研究计划项目（2015JM5172）。

A heterogeneous electro-Fenton-like system with composite cathode Mn₃O₄/ACF for efficient degradation of methylene blue in wide pH range

HE Yingying, MENG Jian, MA Yali, ZHANG Xiaoyu

School of Science, Xi'an University of Architecture and Technology, Xi'an 710055, Shaanxi, China

Received:2016-06-06 Revised:2016-09-29 Online:2017-01-05 Published:2017-01-05
Contact: 10.11949/j.issn.0438-1157.20160775
Supported by:
supported by the National Natural Science Foundation of China (51378414) and Shaanxi Natural Science Foundation Project (2015JM5172).

摘要/Abstract

摘要：

用电化学方法将Mn₃O₄负载于活性炭纤维（activated carbon fiber，ACF）表面制备了Mn₃O₄/ACF复合阴极，与铂丝阳极构成了异相类电芬顿体系对模型污染物亚甲基蓝（MB）进行降解，考察了该体系在不同pH条件下对MB去除率，并对体系中的活性氧物种进行了检测，初步探讨了降解机理。实验结果表明，在pH 3.0、pH 5.0和pH 7.0时亚甲基蓝脱色率分别达到97.3%、99.9%、99.8%，pH5.0时TOC去除率达到88.6%，pH 7.0和pH 3.0时也分别达到了80.4%和73.4%，拓宽了电芬顿反应的适宜pH范围。体系中活性氧物种的检测结果表明，氧在阴极电还原产生H₂O₂，并与Mn₃O₄反应生成羟基自由基·OH，同时，氧的一电子还原产物超氧自由基O₂·^-也对阴极表面污染物的脱色有重要贡献。

关键词: 电解, 催化剂, 复合材料, 类电芬顿, 自由基, 亚甲基蓝, 降解

Abstract:

A composite activated carbon fiber(ACF) cathode Mn₃O₄/ACF, which was prepared using a cyclic voltammetry method, was employed in a heterogeneous electro-Fenton-like system for the degradation of a model dye, methylene blue(MB), with no other reagents added.The decolorization ratio and the mineralization of MB in the different pH were investigated and the active oxygen species involved in the system were also detected.The experiment results showed that when solution pH was set as 3.0, 5.0 and 7.0, the decolorization ratio reached to 97.3%, 99.9% and 99.8%, respectively, and TOC removal achieved to 73.4%, 88.6% and 80.4%, indicating the extensive feasibility of the system in broad pH range.The results of detection of the active oxygen species demonstrated that H₂O₂ was electro-produced at the surface of cathode.The hydroxyl free radical·OH generated by the Fenton-like reaction of Mn₃O₄ with H₂O₂ was responsible to the degradation of MB.The superoxide radical O₂·^- was also proved playing important role in decolorization of MB.The mechanism of degradation of the contaminant by this heterogeneous electro-Fenton-like system was preliminarily discussed.

Key words: electrolysis, catalyst, composite, electro-Fenton-like, free radical, methylene blue, degradation

中图分类号:

何盈盈, 孟建, 马亚利, 张潇予. 宽pH条件下Mn₃O₄/ACF复合阴极类电芬顿体系降解亚甲基蓝[J]. 化工学报, 2017, 68(1): 305-312.

HE Yingying, MENG Jian, MA Yali, ZHANG Xiaoyu. A heterogeneous electro-Fenton-like system with composite cathode Mn₃O₄/ACF for efficient degradation of methylene blue in wide pH range[J]. CIESC Journal, 2017, 68(1): 305-312.

参考文献 26

[1]	SOLPAN D, GUVEN O. Decoloration and degradation of some textile dyes by gammairradiation[J]. Radiat. Phys. Chem., 2002, 65(4):549-558.
[2]	王益平, 钱经纬. Electro-Fenton法处理印染废水应用研究进展[J]. 环境工程, 2014, 32:117-120. WANG Y P, QIAN J W. Applications of electro-Fenton technique in dyeing waste water treatment[J]. Environ. Eng., 2014, 32:117-120.
[3]	NIDHEESH P V, GANDHIMATHI R. Trends in electro-Fenton process for water and wastewater treatment:an overview[J]. Desalination, 2012, 299:1-15.
[4]	WANG A, QU J H, RU J, et al. Mineralization of an azo dye Acid Red 14 by electro-Fenton's reagent using an activated carbon fiber cathode[J]. Dyes. Pigm., 2005, 65:227-233.
[5]	FERNADESRÊGO F E, MARTINEZHUITLE C A. Application of electro-Fenton process as alternative for degradation of novacron blue dye[J]. Environ. Chem. Eng., 2014, 2:875-880.
[6]	WANG C T, CHOU W L, CHUNG M H. COD removal from real dyeing wastewater by electro-Fenton technology using an activated carbon fiber cathode[J]. Desalination, 2010, 253:129-134.
[7]	胡晶晶, 莫文艳, 孙杰. 电芬顿降解活性艳红X3B的阳极影响因素[J]. 化工学报, 2012, 63(11):3694-3699. HU J J, MO W Y, SUN J. Anode effect on X3B degradation in electro-Fenton reaction[J]. CIESC Journal, 2012, 63(11):3694-3699.
[8]	JIA J P, YANG J, LIAO J, et al. Treatment of dyeing wastewater with ACF electrodes[J]. Water Res., 1999, 33:881-884.
[9]	CHEN J X, ZHU L Z. Catalytic degradation of orange Ⅱ by UV-Fenton with hydroxyl-Fe-pillared bentonite in water[J]. Chemosphere, 2006, 65(7):1249-1255.
[10]	FENG J Y, HU X J, YUE P L. Novel bentonite clay-based Fe-nanocomposite as a heterogeneous catalyst for photo-Fenton discoloration and mineralization of orange Ⅱ[J]. Environ. Sci. Technol., 2004, 38(1):269-275.
[11]	FENG J Y, HU X J, YUE P L. Discoloration and mineralization of orange Ⅱ by using a bentonite clay-based Fe nanocomposite film as a heterogeneous photo-Fenton catalyst[J]. Water Res., 2005, 39(1):89-90.
[12]	张国亮. 电解耦合类芬顿多相催化降解水中对硝基酚[D]. 大连:大连理工大学, 2009. ZHANG G L. Study on catalytic decomposition of p-nitrophenol by electro-Fenton-like reaction[D]. Dalian:Dalian University of Technology, 2009.
[13]	LI J P, AI Z H, ZHANG L Z. Design of a neutral electro-Fenton system with Fe@Fe2O3/ACF composite cathode for wastewater treatment[J]. Hazard. Mater., 2009, 164:18-25.
[14]	KHATAEE A R, FATHINIA M, ZAREI M, et al. Modeling and optimization of photo-catalytic/photo-assisted-electro Fenton like degradation of phenol using a neural network coupled with genetic algorithm[J]. J. Ind. Eng. Chem., 2014, 20:1852-1860.
[15]	赵莹. 四氧化三锰纳米粒子的制备与性质研究[D]. 长春:吉林大学, 2011. ZHAO Y. Study on the synthesis and properties of hausmannite nanoparticles[D]. Changchun:Jilin University, 2011.
[16]	ISHIBASHI K, FUJISHMA A, WATANABE T, et al. Detection of active oxidative species in TiO2 photocatalysis using the fluorescence technique[J]. Electrochem. Commun., 2000, 2:207-210.
[17]	魏复盛. 水和废水检测分析方法[M]. 4版. 北京:中国环境出版社, 2002:211-216. WEI F S. Water and Waste Water Detection Analysis Method[M]. 4th ed. Beijing:China Environmental Science Press, 2002:211-216.
[18]	周国伟, 李天铎, 徐桂英, 等. 红钛锰矿MnTiO3纳米材料的溶胶-凝胶法制备及光谱研究[J]. 中国科学, 2004, 34(6):449-453. ZHOU G P, LI T Z, XU G Y, et al. The study of nano-MnTiO3 preparation using sol-gel method and spectroscopic[J]. Chin. Sci. Ser., 2004, 34(6):449-453.
[19]	MOSES E R A, GRACE V S. XRD and XPS characterization of mixed valence Mn3O4 hausmannite thin films prepared by chemical spray pyrolysis technique[J]. Appl. Surf. Sci., 2010, 256:2920-2926.
[20]	LI Y Q, QU J Y, GAO F. In situ fabrication of Mn3O4 decorated graphene oxide as a synergistic catalyst for degradation of methylene blue[J]. Appl. Catal. B:Environ., 2015, 162:268-274.
[21]	古振澳, 柴一荻, 杨乐, 等. 以泡沫镍为阴极的电芬顿法对苯酚的降解[J]. 环境工程学报, 2015, 9(12):5843-5848. GU Z A, CHAI Y D, YANG L, et al. Electro-Fenton degradation of phenol using foam nickel as cathode[J]. Chin. J. Environ. Eng., 2015, 9(12):5843-5848.
[22]	ZHAO H Y, WANG Y J, WANG Y B, et al. Electro-Fenton oxidation of pesticides with a novel Fe3O4@Fe2O3/activated carbon aerogel cathode:high activity, wide pH range and catalytic mechanism[J]. Appl. Catal. B:Environ., 2012, 125:120-127.
[23]	程丽华, 黄君礼, 倪福祥. Fenton试剂生成·OH的动力学研究[J]. 环境工程学报, 2003, 4(5):12-15. CHENG L H, HUANG J L, NI F X. Generation kinetics of hydroxyl radicals by Fenton's reagent[J]. Chin. J. Environ. Eng., 2003, 4(5):12-15.
[24]	SUN M, RU X R, ZHAI L F. In-situ fabrication of supported iron oxides from synthetic acid mine drainage:high catalytic activities and good stabilities towards electro-Fenton reaction[J]. Appl. Catal., 2015, 165:103-110.
[25]	TAMMEVESKI K, KONTTURI K, NICHOLS R J, et al. Surface redox catalysis for O2 reduction on quinone-modified glassy carbon electrodes[J]. Electroanal. Chem., 2001, 515:101-112.
[26]	IRMAK S, YAVUZ H I, ERBATUR O. Degradation of 4-chloro-2-methyphenol in aqueous solution by electro-Fenton and photoelectro-Fenton processes[J]. Appl. Catal. B:Environ., 2006, 63(3/4):243-248.

宽pH条件下Mn₃O₄/ACF复合阴极类电芬顿体系降解亚甲基蓝

A heterogeneous electro-Fenton-like system with composite cathode Mn₃O₄/ACF for efficient degradation of methylene blue in wide pH range

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献 26

相关文章 15

编辑推荐

Metrics

本文评价

[1]	黄琮琪, 吴一梅, 陈建业, 邵双全. 碱性电解水制氢装置热管理系统仿真研究[J]. 化工学报, 2023, 74(S1): 320-328.
[2]	胡超, 董玉明, 张伟, 张红玲, 周鹏, 徐红彬. 浓硫酸活化五氧化二钒制备高浓度全钒液流电池正极电解液[J]. 化工学报, 2023, 74(S1): 338-345.
[3]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[4]	康飞, 吕伟光, 巨锋, 孙峙. 废锂离子电池放电路径与评价研究[J]. 化工学报, 2023, 74(9): 3903-3911.
[5]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[6]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[7]	杨百玉, 寇悦, 姜峻韬, 詹亚力, 王庆宏, 陈春茂. 炼化碱渣湿式氧化预处理过程DOM的化学转化特征[J]. 化工学报, 2023, 74(9): 3912-3920.
[8]	尹刚, 李伊惠, 何飞, 曹文琦, 王民, 颜非亚, 向禹, 卢剑, 罗斌, 卢润廷. 基于KPCA和SVM的铝电解槽漏槽事故预警方法[J]. 化工学报, 2023, 74(8): 3419-3428.
[9]	李锦潼, 邱顺, 孙文寿. 煤浆法烟气脱硫中草酸和紫外线强化煤砷浸出过程[J]. 化工学报, 2023, 74(8): 3522-3532.
[10]	胡兴枝, 张皓焱, 庄境坤, 范雨晴, 张开银, 向军. 嵌有超小CeO₂纳米粒子的碳纳米纤维的制备及其吸波性能[J]. 化工学报, 2023, 74(8): 3584-3596.
[11]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[12]	李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.
[13]	杨欣, 彭啸, 薛凯茹, 苏梦威, 吴燕. 分子印迹-TiO₂光电催化降解增溶PHE废水性能研究[J]. 化工学报, 2023, 74(8): 3564-3571.
[14]	张蒙蒙, 颜冬, 沈永峰, 李文翠. 电解液类型对双离子电池阴阳离子储存行为的影响[J]. 化工学报, 2023, 74(7): 3116-3126.
[15]	余娅洁, 李静茹, 周树锋, 李清彪, 詹国武. 基于天然生物模板构建纳米材料及集成催化剂研究进展[J]. 化工学报, 2023, 74(7): 2735-2752.