核壳Fenton催化剂CuFe2O4@PDA-Cu的制备、表征及其活化H2O2降解染料的性能

doi:10.3785/j.issn.1008-9497.2018.04.012

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摘要为得到新型高效多相催化剂，有效去除废水中的染料，以Cu（Ac）₂与CuFe₂O₄@PDA为原料制备了催化剂CuFe₂O₄@PDA-Cu.通过IR、XRD、XPS、UV-Vis、DRS技术对催化剂的性能进行了表征，考察了温度、H₂O₂用量、催化剂用量、pH值、盐等对催化活性的影响.利用HPLC测定降解产物，采用自由基捕获和抑制实验进行机理验证，发现催化剂是核壳结构.温度升高、pH值升高、H₂O₂和催化剂用量的增加均有利于提高催化活性；氯化物、硫酸盐、硝酸盐和磷酸盐不影响催化效果，溴化物和亚硝酸盐降低了催化效果.得到的最优降解条件为：T=30 ℃，催化剂用量 10 mg·L^-1，pH=9，过氧化氢用量 10 mmol·L^-1，染料浓度30 mg·L^-1.最优条件下催化剂可循环使用4次以上；甲基橙、茜素红和罗丹明B的去除率为100%；染料R0213、O0118和B0115的去除率大于60%.降解产物有草酸、马来酸和CO₂.甲基橙、茜素红和罗丹明B降解后COD_Mn=2~4 mg·L^-1.水杨酸捕获·OH生成2.5-二羟基苯甲酸，叔丁醇抑制染料降解.结果表明，催化剂可活化H₂O₂产生·OH，·OH攻击染料分子开环降解直至矿化.该研究为开发高效多相催化剂，有效去除废水中的染料提供了科学依据.

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	江银枝
	李静
	袁辉强
	陈燕慧

关键词 ：废水处理, 核壳结构, 多相Fenton催化, 染料降解, 自由基

Abstract：Novel and high-efficiency heterogeneous catalysts are in demand to remove the dye from the wastewater effectively. This paper proposes a catalyst, CuFe₂O₄@PDA-Cu, which was prepared from Cu(Ac)₂ and CuFe₂O₄@PDA. It was characterized by IR spectra, X-ray diffraction, UV-Vis DRS and XPS and its catalytic activity was investigated with different temperature, catalyst dosage, H₂O₂ dosage, pH value and salts while the mechanisms were validated by free radical inhibition and free radical captured experiments. It is found that (1) CuFe₂O₄@PDA-Cu is of core-shell structure, on which the Cu²⁺ is immobilized with coordination bond. (2) Higher temperature, higher H₂O₂ dosage, higher catalyst dosage are favorable for catalytic activity. The higher pH is favorable for catalytic activity under pH=2~10. The catalytic effect is not affected in presence of chloride, sulfate, phosphate and nitrate, but reduced in presence of bromide and nitrite. The optimal experimental condition was T=30℃, the catalyst dosage 10 mg·L^-1, pH=9, 10 mmol·L^-1 H₂O₂ and 30 mg·L^-1 dye. The catalyst could be reused four times with methyl orange degradation of 95%. (3) Methyl orange, alizarin red and rhodamine B were removed with 100% degradation. And dyes containing bromine or nitro group, RO213, O0118, B0115 were removed with above 60% degradation in 24 h. The degradation products were found to have oxalic acid, maleic acid, CO₂, COD_Mn=2~4 mg·L^-1. (4) 2.5-dihydroxybenzoic acid was formed from salicylic acid and hydroxyl radicals, and the dye degradation was inhibited in the presence of tert-butanol. All these indicated that the catalyst with core-shell structure could activate H₂O₂ with the product hydroxyl radical effectively. And the dye molecular should be oxidized and degraded, even mineralized by hydroxyl radical in presence of salts, acid or base with pH<10. This study provides scientific supports to design and prepare highly efficient heterogeneous Fenton catalysts for the effective removal of dyes.

Key words： wastewater treatment core-shell structure heterogeneous Fenton catalysis dye degradation free radical

收稿日期: 2017-09-12

ZTFLH:

O643.3

基金资助:国家自然科学基金资助项目（21472174，21602201）.

作者简介: 江银枝(1973-),ORCID:http://orcid.org/0000-0003-2393-9654,女,博士,副教授,主要从事配位化学、分析化学研究,E-mail:jiangyinzhi@zstu.edu.cn.

引用本文:

江银枝, 李静, 袁辉强, 陈燕慧. 核壳Fenton催化剂CuFe₂O₄@PDA-Cu的制备、表征及其活化H₂O₂降解染料的性能[J]. 浙江大学学报（理学版）, 2018, 45(4): 450-460.
JIANG Yinzhi, LI Jing, YUAN Huiqiang, CHEN Yanhui. Core-shell Fenton catalyst CuFe₂O₄@PDA-Cu: Preparation, characterization and property in dye degradation by activated H₂O₂.. Journal of ZheJIang University(Science Edition), 2018, 45(4): 450-460.

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http://www.zjujournals.com/sci/CN/10.3785/j.issn.1008-9497.2018.04.012 或 http://www.zjujournals.com/sci/CN/Y2018/V45/I4/450

[1] 任南琪, 周显娇, 郭婉茜, 等. 染料废水处理技术研究进展[J]. 化工学报, 2013, 64(1):84-94. REN N Q, ZHOU X J, GUO W X, et al. A review on treatment methods of dye wastewater[J]. CIESC Journal, 2013, 64(1):84-94.
[2] 梁波, 徐金球, 关杰,等. 生物法处理印染废水的研究进展[J]. 化工环保, 2015, 35(3):259-266. LIANG B, XU J Q, GUAN J, et al. Research progresses in treatment of dyeing wastewater by biological methods[J]. Environmental Protection of Chemical Industry, 2015, 35(3):259-266.
[3] GLAZE W H, KANG J W, CHAPIN D H. The chemistry of water treatment processes involving ozone, hydrogen peroxide and ultraviolet radiation[J]. Ozone Science & Engineering, 1987, 9(4):335-352.
[4] OTURAN M A, AARON J J. Advanced oxidation processes in water/wastewater treatment:Principles and applications-A review[J]. Critical Reviews in Environmental Science and Technology, 2014, 44(23):2577-2641.
[5] 孙怡, 于利亮, 黄浩斌, 等.高级氧化技术处理难降解有机废水的研发趋势及实用化进展[J].化工学报, 2017, 68(5):1743-1756. SUN Y, YU L L, HUANG H B, et al. Research trend and practical development of advanced oxidation process on degradation of refractory organic wastewater[J]. CIESC Journal, 2017, 68(5):1743-1756.
[6] MIRZAEI A, CHEN Z, HAGHIGHAT F, et al. Removal of pharmaceuticals from water by homo/heterogonous Fenton-type processes-A review[J].Chemosphere, 2017, 174(2):665-688.
[7] RACHE M L, GARCÍA A R, ZEA H R, et al. Azo-dye orange Ⅱ degradation by the heterogeneous Fenton-like process using a zeolite Y-Fe catalyst-Kinetics with a model based on the Fermi's equation[J]. Applied Catalysis B(Environmental), 2014, 146(1):192-200.
[8] 柴凡凡, 李克艳, 郭新闻. 非均相催Fenton化剂的组成结构设计与性能优化[J].应用化学, 2016, 33(2):133-143. CHAI F F, LI K Y, GUO X W. Composition and structural design for high performance heterogeneous Fenton catalysts[J]. Chinese Journal of Applied Chemistry, 2016, 33(2):133-143.
[9] LI R, JIN X, MEGHARAJ M, et al. Heterogeneous Fenton oxidation of 2, 4-dichlorophenol using iron-based nanoparticles and persulfate system[J]. Chemical Engineering Journal, 2015, 264(2):587-594.
[10] ESTEVES B M, RODRIGUES C S, BOAVENTURA R A, et al. Coupling of acrylic dyeing wastewater treatment by heterogeneous Fenton oxidation in a continuous stirred tank reactor with biological degradation in a sequential batch reactor[J]. Journal of Environmental Management, 2016, 166(1):193-203.
[11] GHIME D, GHOSH P. Heterogeneous Fenton degradation of oxalic acid by using silica supported iron catalysts prepared from raw rice husk[J]. Journal of Water Process Engineering, 2017, 19(1):156-163.
[12] 孙宏, 张泽, 王艳悦. 铁酸铜催化氧化水体中的苯酚[J]. 化学世界, 2016, 57(2):98-100. SUN H,ZHANG Z,WANG Y Y. Catalytic oxidation of phenol in water with CuFe₂O₄[J]. Chemistry World, 2016, 57(2):98-100.
[13] GÓMEZ-PASTORA J, BRINGAS E, ORTIZ I. Recent progress and future challenges on the use of high performance magnetic nano-adsorbents in environmental applications[J]. Chemical Engineering Journal, 2014, 256(8):187-204.
[14] GE R, LI X, LIN M, et al. Fe₃O₄@polydopamine composite theranostic superparticles employing preassembled Fe₃O₄ nanoparticles as the core[J]. Applied Materials & Interfaces,2016, 8(35):22942-22952.
[15] MA S, FENG J, QIN W, et al. CuFe₂O₄@PDA magnetic nanomaterials with a core-shell structure:Synthesis and catalytic application in the degradation of methylene blue in water[J]. Rsc Advances,2015, (66)5:53514-53523
[16] 江银枝, 时永强, 史银瓶, 等. 双水杨醛缩二乙烯三胺Cu(Ⅱ)配合物的合成及催化染料降解性能[J].中国科学化学, 2014, 44(10):1528-1535. JIANG Y Z, SHI Y Q, SHI Y P, et al. Synthesis and dye degradation performance of the complex of Cu(Ⅱ) with bis-salicylidene diethylenetriamine Schiff bases[J]. Scientia Sinica Chimica, 2014, 44(10):1528-1535.
[17] 江银枝, 赵攻城, 时永强, 等. 氨基乙醇席夫碱配合物的合成及其催化染料降解[J]. 环境科学学报, 2016, 36(3):893-899. JIANG Y Z, ZHAO G C, SHI Y Q, et al. Cu²⁺ complexes with 2-aminoethanol schiff base:synthesis and catalytic performance for degradation of dyes degradation[J]. Acta Scientiae Circumstantiae, 2016, 36(3):893-899.
[18] GLIGOROVSKI S, STREKOWSKI R, BARBATI S, et al. Environmental implications of hydroxyl radicals (OH)[J]. Chemical Reviews, 2015, 115(24):13054-13062.