钒掺杂铜基、铁基双金属催化剂的非均相芬顿氧化性能

doi:10.16085/j.issn.1000-6613.2021-0082

摘要/Abstract

摘要：

为了合理设计有效的非均相芬顿催化剂，本研究采用溶剂热法合成了两种钒掺杂双金属催化剂，并比较了它们的非均相芬顿降解亚甲基蓝的性能。还通过扫描电子显微镜（SEM）、X射线衍射（XRD）、X射线光电子能谱（XPS）等技术手段对样品进行了表征。结果显示，两种催化剂对酸性到碱性（pH=3~10）的亚甲基蓝溶液均有较好的降解效果，Cu-V复合材料在pH=10时对亚甲基蓝的去除率最高，达到95.60%；Fe-V复合材料在pH=3时对亚甲基蓝的去除率最高，达到96.60%。Cu-V、Fe-V复合材料均具有良好的重复利用性，在pH=7的条件下连续运行六次后，对亚甲基蓝的去除率仍分别保持在79.16%和68.22%。对催化反应体系的机理进行了初步探讨，羟基自由基是主要的活性物种，两种催化剂的催化机理略有不同。

关键词: 双金属催化剂, 非均相 Fenton, 协同作用, 废水, 机制

Abstract:

This study used solvothermal method to synthesize two vanadium-doped bimetallic catalysts, and compared their heterogeneous Fenton degradation performance of Methylene blue. The samples were characterized by SEM, XRD, XPS, etc. The two catalysts showed good capacities for degradation of Methylene blue in both acidic to alkaline solutions (pH=3—10). The highest removal rate of Methylene blue by the Cu-V composite material was 95.60% at pH=10, while that by the Fe-V composite material reached 96.6% at pH=3. Both the Cu-V and Fe-V composite materials had good reusability. After six consecutive runs at pH=7, the removal rate of methylene blue remained at 79.16% and 68.22%, respectively. The mechanism of the catalytic reaction system has been preliminarily discussed. The hydroxyl radical is the main active species, but the catalytic mechanisms of the two catalysts are slightly different.

Key words: bimetallic catalyst, heterogeneous Fenton, synergy, waste water, mechanism

中图分类号:

TQ426.82

王斌, 杨月红, 阳耀熙. 钒掺杂铜基、铁基双金属催化剂的非均相芬顿氧化性能[J]. 化工进展, 2021, 40(12): 6705-6713.

WANG Bin, YANG Yuehong, YANG Yaoxi. Heterogeneous Fenton oxidation performance of vanadium-doped copper-based and iron-based bimetallic catalysts[J]. Chemical Industry and Engineering Progress, 2021, 40(12): 6705-6713.

图/表 13

图1 不同V掺杂量对MB脱色率的影响

图2 不同V掺杂量材料的Cu 2p高分辨率光电子能谱

图3 裸Cu、Cu-V、裸Fe和Fe-V的SEM图片

图4 裸Cu、Cu-V、裸Fe、Fe-V的XRD图谱

图5 XPS分析的合成材料元素的价态

图6 不同反应体系对MB脱色率的影响

表1 部分双金属复合催化剂芬顿性能比较

催化剂种类	反应条件	脱色率/%	出处
SAC-Fe/Cu-500℃	MB 100mg/L，催化剂 0.1g/L，H₂O₂ 6mL/L，pH=7，T=25℃	27	［25］
Fe-Cu-080	MB 5mg/L，催化剂 0.05g/L，H₂O₂ 5%，pH=7，T=25℃	＞99	［26］
MgFe-LDH	MB 20mg/L，催化剂 2.0g/L，H₂O₂ 1mL，pH=7，T=25℃	78.2	［27］
Cu-V	MB 100mg/L，催化剂 0.5g/L，H₂O₂ 10mmol/L，pH=7，T=25℃	88.32	本文
Fe-V	MB 100mg/L，催化剂 0.5g/L，H₂O₂ 10mmol/L，pH=7，T=25℃	75.27	本文

图7 催化剂用量对MB脱色率的影响

图8 H2O2用量对MB脱色率的影响

图9 pH对MB脱色率的影响

图10 催化剂重复使用对MB脱色率的影响

图11 淬灭反应

图12 Cu-V/H2O2、Fe-V/H2O2体系降解MB的机理示意图

参考文献 32

1	HE Jie, YANG Xiaofang, Bin MEN, et al. Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials: a review [J]. Journal of Environmental Sciences, 2016, 39: 97-109.
2	WANG Qing, MA Yuan, XING Shengtao. Comparative study of Cu-based bimetallic oxides for Fenton-like degradation of organic pollutants[J]. Chemosphere, 2018, 203: 450-456.
3	LOVJEET Singh, PAWAN Rekha, SHRI Chand. Comparative evaluation of synthesis routes of Cu/zeolite Y catalysts for catalytic wet peroxide oxidation of quinoline in fixed-bed reactor[J]. Journal of Environmental Management, 2018, 215: 1-12.
4	JIANG Songshan, ZHANG Huiping, YAN ZhangYing. Cu-MFI zeolite supported on paper-like sintered stainless fiber for catalytic wet peroxide oxidation of phenol in a batch reactor[J]. Separation and Purification Technology, 2018, 190: 243-251.
5	PAN Yue, JIANG Songshan, XIONG Wei, et al. Supported CuO catalysts on metal-organic framework (Cu-UiO-66) for efficient catalytic wet peroxide oxidation of 4-chlorophenol in wastewater[J]. Microporous and Mesoporous Materials, 2020, 291: 109703.
6	WANG Songxue, TIAN Jiayu, WANG Qiao, et al. Development of CuO coated ceramic hollow fiber membrane for peroxymonosulfate activation: a highly efficient singlet oxygen-dominated oxidation process for bisphenol a degradation[J]. Applied Catalysis B: Environmental, 2019, 256: 117783.
7	XIANG Wei, ZHOU Tao, WANG Yifan. Catalytic oxidation of diclofenac by hydroxylamine-enhanced Cu nanoparticles and the efficient neutral heterogeneous-homogeneous reactive copper cycle[J]. Water Research, 2019, 153: 274-283.
8	SU Zhen, LI Jing, ZHANG Dandan, et al. Novel flexible Fenton-like catalyst: unique CuO nanowires arrays on copper mesh with high efficiency across a wide pH range[J]. Science of the Total Environment, 2019, 647: 587–596.
9	ZHANG Nuanqin, XUE Chengjie, WANG Kuang, et al. Efficient oxidative degradation of fluconazole by a heterogeneous Fenton process with Cu-V bimetallic catalysts[J]. Chemical Engineering Journal, 2020, 380: 122516.
10	ZHU Yanping, ZHU Runliang, XI Yunfei, et al. Strategies for enhancing the heterogeneous Fenton catalytic reactivity: a review[J]. Applied Catalysis B: Environmental, 2019, 255: 117739.
11	ZHANG Nuanqin, YI Yunqiang, LIAN Jintao, et al. Effects of Ce doping on the Fenton-like reactivity of Cu-based catalyst to the fluconazole[J]. Chemical Engineering Journal, 2020, 395: 124897.
12	李家欣, 张宝刚, 高玥琪, 等. 钒系催化剂在环境保护中的应用研究进展[J]. 环境科学与技术, 2020, 43(6): 179-189.
	LI Jiaxin, ZHANG Baogang, GAO Yueqi, et al. Research progress on the application of vanadium based catalyst in environmental protection[J]. Environmental Science & Technology, 2020, 43(6): 179-189.
13	REN Xiaohua, LIU Yang, GUO Weilin, et al. Morphology and crystal facet-dependent activation mechanism of persulfate by V₂O₅ nanomaterials for organic pollutants degradation[J]. Separation and Purification Technology, 2020, 253: 117501.
14	FANG Guodong, DENG Yamei, HUANG Min, et al. A mechanistic understanding of hydrogen peroxide decomposition by vanadium minerals for diethyl phthalate degradation[J]. Environmental Science Technology, 2018, 52: 2178-2185.
15	RYAN R L, DAVID M K, CHRISTOPHER L M, et al. Catalytic applications of vanadium: a mechanistic perspective[J]. Chemical Reviews, 2019, 119: 2128-2191.
16	LAI Leiduo, ZHOU Hongyu, LAI Bo. Heterogeneous degradation of bisphenol A by peroxymonosulfate activated with vanadium-titanium magnetite: performance, transformation pathways and mechanism[J]. Chemical Engineering Journal, 2018, 349: 633–645.
17	DENG Jingheng, JIANG Jingyuan, ZHANG Yuanyuan, et al. FeVO₄ as a highly active heterogeneous Fenton-like catalyst towards the degradation of Orange Ⅱ[J]. Applied Catalysis B: Environmental, 2008, 84: 468-473.
18	孙浩, 吴娟, 马东, 等. 钒酸铁类Fenton催化剂的制备及性能研究[J]. 中国环境科学, 2015, 35(6): 1734-1739.
	SUN Hao, WU Juan, MA Dong, et al. Preparation of iron (Ⅲ) vanadate Fenton-like catalyst and its catalytic performance[J]. China Environmental Science, 2015, 35(6): 1734-1739.
19	SUN Yang, TIAN Pengfei, DING Doudou, et al. Revealing the active species of Cu-based catalysts for heterogeneous Fenton reaction[J]. Applied Catalysis B: Environmental, 2019, 258: 117985.
20	WANG Jing, LIU Chao, FENG Jiayou, et al. MOFs derived Co/Cu bimetallic nanoparticles embedded in graphitized carbon nanocubes as efficient Fenton catalysts[J]. Journal of Hazardous Materials, 2020, 394: 122567.
21	ZHANG Yuting, LIU Cao, XU Bingbing, et al. Degradation of benzotriazole by a novel Fenton-like reaction with mesoporous Cu/MnO₂: combination of adsorption and catalysis oxidation[J]. Applied Catalysis B: Environmental, 2016, 199: 447-457.
22	LI Zhenlu, Jianchang LYU, GE Ming, et al. Synthesis of magnetic Cu/CuFe₂O₄ nanocomposite as a highly efficient Fenton-like catalyst for methylene blue degradation[J]. Journal of Materials Science, 2018, 53:15081-15095.
23	宋文臣, 李宏, 张勇健, 等. X射线光电子能谱分析钒渣熟料中钒的价态[J]. 冶金分析, 2014, 34(4): 27-71.
	SONG Wencheng, LI Hong, ZHANG Yongjian, et al. Analysis of the valence state of vanadium in vanadium slag clinker by X-ray photoelectron spectroscopy[J]. Metallurgical Analysis, 2014, 34(4): 27-71.
24	WAN Zhong, WANG Jianlong. Degradation of sulfamethazine antibiotics using Fe₃O₄-Mn₃O₄ nanocomposite as a Fenton-like catalyst[J]. Journal of Chemical Technology & Biotechnology, 2017, 92: 874-883.
25	郭晋邑. 造纸污泥活性炭在非均相Fenton体系中的应用研究[D]. 杭州: 浙江大学, 2016.
	GUO Jinyi. Application research of paper mill sludge-derived activated carbon in heterogeneous Fenton[D]. Hangzhou: Zhejiang University, 2016.
26	THANH Binh Nguyen, CHENG Didong, HUANG C P, et al. Fe-Cu bimetallic catalyst for the degradation of hazardous organic chemicals exemplified by methylene blue in Fenton-like reaction[J]. Journal of Environmental Chemical Engineering, 2020, 8: 104139.
27	ROSEMBERGUE Gabriel Lima Gonçalves, HANA Moreira Mendes, SIBELE Lima Bastos, et al. Fenton-like degradation of methylene blue using Mg/Fe and MnMg/Fe layered double hydroxides as reusable catalysts[J]. Applied Clay Science, 2020, 187: 105477.
28	WAN Zhong, WANG Jianlong. Degradation of sulfamethazine using Fe₃O₄-Mn₃O₄/reduced graphene oxide hybrid as Fenton-like catalyst[J]. Journal of Hazardous Materials, 2017, 324: 653-664.
29	WANG Jianlong, XU Lejin. Advanced oxidation processes for wastewater treatment: formation of hydroxyl radical and application[J]. Critical Reviews in Environmental Science and Technology, 2012, 42: 251-325.
30	SAMIA Ben Hammouda, ZHAO Feiping, ZAHRA Safaei, et al. Reactivity of novel ceria-perovskite composites CeO₂-LaMO₃ (MCu, Fe) in the catalytic wet peroxidative oxidation of the new emergent pollutant “Bisphenol F”: characterization, kinetic and mechanism studies[J]. Applied Catalysis B: Environmental, 2017, 218: 119-136.
31	Le-Tuan Pham ANH, Doyle FIONA M, Sedlak DAVID L. Kinetics and efficiency of H₂O₂ activation by iron-containing minerals and aquifer materials[J]. Water Research, 2012, 46: 6454 -6462.
32	MAO Jie, QUAN Xie, WANG Jing, et al. Enhanced heterogeneous Fenton-like activity by Cu-doped BiFeO₃ perovskite for degradation of organic pollutants[J]. Frontiers Environmental Science & Engineering, 2018, 12(6): 10.

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