Cux-Bi25FeO40活化过硫酸盐降解水中磺胺嘧啶研究

doi:10.16258/j.cnki.1674-5906.2024.12.009

生态环境学报 ›› 2024, Vol. 33 ›› Issue (12): 1914-1922.DOI: 10.16258/j.cnki.1674-5906.2024.12.009

• 研究论文【环境科学】 • 上一篇下一篇

Cu_x-Bi₂₅FeO₄₀活化过硫酸盐降解水中磺胺嘧啶研究

丛鑫¹(), 王晓博¹, 姜久宁²

1.辽宁工程技术大学环境科学与工程学院，辽宁阜新 123000
2.中国恩菲工程技术有限公司，北京 100038

收稿日期:2024-09-21 出版日期:2024-12-18 发布日期:2024-12-31
作者简介:丛鑫（1976年生）女，教授，博士，研究方向为土壤环境化学和生态修复。E-mail: congxin1800@163.com
基金资助:
国家自然科学基金项目(41403100)

Degradation of Sulfadiazine by Cu_x-Bi₂₅FeO₄₀Activated Persulfate

CONG Xin¹(), WANG Xiaobo¹, JIANG Jiuning²

1. College of Environmental Science and Engineering, Liaoning Technical University, Fuxin 123000, P. R. China
2. China ENFI Engineering Corporation, Beijing 100038, P. R. China

Received:2024-09-21 Online:2024-12-18 Published:2024-12-31

摘要/Abstract

摘要：

以环境风险较高的磺胺嘧啶（SD）污染物为研究对象，通过水热合成法制备金属Cu掺杂的Cu_x-Bi₂₅FeO₄₀铁酸铋复合材料，将其用于活化过硫酸盐（PS）降解水体中SD。该研究系统地分析了Cu_x-Bi₂₅FeO₄₀/PS体系中铜铁掺杂物质的量比、复合材料投加质量浓度、PS浓度、溶液pH及反应温度等因素对SD降解率的影响。实验结果表明，在反应时间为1 h，铜铁掺杂摩尔比1꞉1条件下，铁酸铋活化PS体系中SD降解效果要优于其余掺杂比例。实验条件下，反应溶液初始pH值由3增长到7，水体中SD的降解率增加了64.1%，降解率的增幅要高于其他3种影响因素。单因素优化实验结果表明，在Cu-Bi₂₅FeO₄₀的投加质量浓度为0.4 g∙L⁻¹、PS浓度为4 mmol·L⁻¹、pH值为5、反应温度为55 ℃的实验条件下，Cu-Bi₂₅FeO₄₀/PS反应体系中SD的降解率最高。为分析各因素及其交互作用对水体中SD降解率的影响，采用Box-Behnken响应面法，建立了以PS浓度、温度和pH值为变量的二次多项式回归模型，通过模型预测得到SD的最佳降解条件为，PS浓度5.1 mmol·L⁻¹、pH值6.6、温度52 ℃，在此条件下SD的降解率达到96.7%。模型预测值与实验验证结果的相对偏差小于5%，证实了模型的可靠性，此模型可以用于对Cu-Bi₂₅FeO₄₀/PS体系中SD降解率的预测。该研究为铁酸铋材料活化过硫酸处理水环境中SD污染提供了理论依据和技术支持。

关键词: 磺胺嘧啶, 铜掺杂铁酸铋, 过硫酸盐, 响应面优化, 水环境

Abstract:

This study focuses on the issue of sulfonamide antibiotic pollution in aquatic environments, targeting the pollutant sulfadiazine (SD), which has a higher environmental risk. A Cu-doped Cu_x-Bi₂₅FeO₄₀ bismuth ferrite composite material was prepared using a hydrothermal synthesis method and used to activate persulfate (PS) for the degradation of SD in water bodies. This study systematically analyzed the impact of factors such as the copper-iron doping molar ratio, composite material dosage, PS concentration, solution pH, and reaction temperature on the SD degradation rate of the Cu_x-Bi₂₅FeO₄₀/PS system. The experimental results showed that under a reaction time of 1 h and a copper-iron doping molar ratio of 1꞉1, the SD degradation effect in the PS system activated by bismuth ferrite was higher than that of the other doping ratios. Under the experimental conditions, as the initial pH of the reaction solution increased from 3 to 7, the degradation rate of SD in the water body increased by 64.1%, which was higher than that of the other three influencing factors. Single-factor optimization experimental results indicated that under the experimental conditions of a Cu-Bi₂₅FeO₄₀dosage of 0.4 g·L⁻¹, PS concentration of 4 mmol·L⁻¹, pH of 5, and reaction temperature of 55 ℃, the SD degradation rate in the Cu-Bi₂₅FeO₄₀/PS reaction system was the highest. To analyze the impact of these factors and their interactive effects on the SD degradation rate in water, the Box-Behnken response surface method was used to establish a quadratic polynomial regression model with PS concentration, temperature, and pH value as variables. The model predicted the optimal degradation conditions for SD as a PS concentration of 5.1 mmol·L⁻¹, a pH value of 6.6, and a temperature of 52 ℃, achieving a degradation rate of 96.7%. The relative deviation between the experimental verification results and the model predictions was less than 5%, confirming the reliability of the model, which can be used to predict the SD degradation rate in the Cu-Bi₂₅FeO₄₀/PS system. This study provides a theoretical basis and technical support for the treatment of SD pollution in aquatic environments using PS-activated bismuth ferrite.

Key words: sulfadazine, copper-doped bismuth ferrite, persulfate, response surface optimization, aquatic environment

中图分类号:

丛鑫, 王晓博, 姜久宁. Cu_x-Bi₂₅FeO₄₀活化过硫酸盐降解水中磺胺嘧啶研究[J]. 生态环境学报, 2024, 33(12): 1914-1922.

CONG Xin, WANG Xiaobo, JIANG Jiuning. Degradation of Sulfadiazine by Cu_x-Bi₂₅FeO₄₀Activated Persulfate[J]. Ecology and Environment, 2024, 33(12): 1914-1922.

图/表 13

表1 响应面实验设计

Table 1 Design plan of response surface optimization test

实验水平	实验因素
实验水平	A: PS浓度/(mmol·L⁻¹)	B: 摄氏温度/℃	C: pH
−1	2	25	5
0	4	40	7
1	6	55	9

图1 Bi25FeO40及Cu-Bi25FeO40的XRD图

Figure 1 XRD images of Bi25FeO40 and Cu-Bi25FeO40

图2 Bi25FeO40及Cu-Bi25FeO40的扫描电镜图

Figure 2 SEM images of Bi25FeO40 and Cu-Bi25FeO40

图3 不同金属掺杂比例条件Cux-Bi25FeO40/PS反应体系中SD降解曲线

Figure 3 Degradation curves of SD in Cux-Bi25FeO40/PS reaction system under different metal doping ratios

图4 不同温度条件下Cu-Bi25FeO40/PS反应体系中SD降解曲线

Figure 4 Degradation curves of SD in Cu-Bi25FeO40/PS reaction system under different temperature

图5 不同pH条件下Cu-Bi25FeO40/PS反应体系中SD降解曲线

Figure 5 Degradation curves of SD in Cu-Bi25FeO40/PS reaction system under different pH

图6 不同Cu-Bi25FeO40浓度条件下反应体系中SD降解曲线

Figure 6 Degradation curves of SD in reaction system under different Cu-Bi25FeO40 concentrations

图7 不同PS浓度条件下Cu-Bi25FeO40/PS反应体系中SD降解曲线

Figure 7 Degradation curves of SD in Cu-Bi25FeO40/PS reaction system under different PS concentrations

表2 响应面实验设计与实验结果

Table 2 Experimental design and experimental results of response surface analysis

实验序号	pH	摄氏温度/℃	PS浓度/(mmol·L⁻¹)	降解率/%
1	7	55	6	0.966
2	7	40	4	0.953
3	7	25	2	0.918
4	7	40	4	0.959
5	7	25	6	0.945
6	7	40	4	0.949
7	7	40	4	0.954
8	9	40	6	0.942
9	5	40	6	0.946
10	9	55	4	0.949
11	7	55	2	0.942
12	9	25	4	0.930
13	5	40	2	0.910
14	9	40	2	0.929
15	5	55	4	0.9544
16	7	40	4	0.955
17	5	25	4	0.908

表3 回归模型方差分析

Table 3 Variance analysis of the regression model

方差来源	模型	A	B	C	AB	AC	BC	失拟项
平方和	4.56×10⁻³	1.21×10⁻⁴	1.52×10⁻³	1.29×10⁻³	1.88×10⁻⁴	1.38×10⁻⁴	2.72×10⁻⁶	4.77×10⁻⁵
自由度	9	1	1	1	1	1	1	3
均方	5.06×10⁻⁴	1.21×10⁻⁴	1.52×10⁻³	1.29×10⁻³	1.88×10⁻⁴	1.38×10⁻⁴	2.72×10⁻⁶	1.59×10⁻⁵
F值	35.1	8.39	106	89.6	13.0	9.58	0.189	1.20
p值	<0.0001	0.0231	<0.0001	<0.0001	0.0086	0.0174	0.6768	0.4176
显著性	极显著	显著	极显著	极显著	极显著	显著	不显著	不显著

图8 溶液pH和反应温度交互作用对SD降解率的影响

Figure 8 Effect of the interaction between solution pH and reaction temperature on the SD degradation rate

图9 溶液pH和PS浓度交互作用对SD降解率的影响

Figure 9 Effect of the interaction of solution pH and PS concentrations on the SD degradation rate

图10 反应温度和PS浓度交互作用对SD降解率的影响

Figure 10 Effect of the interaction between reaction temperature and PS concentration on the SD degradation rate

参考文献 39

[1]	CHENG M, ZENG G M, HUANG D L, et al., 2018. Efficient degradation of sulfamethazine in simulated and real wastewater at slightly basic pH values using Co-SAM-SCS/H₂O₂ Fenton-like system[J]. Water Research, 138: 7-18.
[2]	GUAN Y H, MA J, LI X C, et al., 2011. Influence of pH on the formation of sulfate and hydroxyl radicals in the UV/peroxymonosulfate system[J]. Environmental Science & Technology, 45(21): 9308-9314.
[3]	LI L, LIU D, ZHANG Q, et al., 2019. Occurrence and ecological risk assessment of selected antibiotics in the freshwater lakes along the middle and lower reaches of Yangtze River Basin[J]. Journal of Environmental Management, 249: 109396.
[4]	LI S, WU Y N, ZHENG H S, et al., 2022. High microwave responsivity Co-Bi₂₅FeO₄₀ in synergistic activation of peroxydisulfate for high efficiency pollutants degradation and disinfection: Mechanism of enhanced electron transfer[J]. Chemosphere, 288(Part 2): 132558.
[5]	LI S, ZHANG G S, ZHANG W, et al., 2017b. Microwave enhanced Fenton-like process for degradation of perfluorooctanoic acid (PFOA) using Pb-BiFeO₃/rGO as heterogeneous catalyst [J]. Chemical Engineering Journal, 326: 756-764.
[6]	LI S, ZHANG G S, ZHENG H S, et al., 2017a. Stability of BiFeO₃: nanoparticles via microwave-assisted hydrothermal synthesis in Fenton-like process[J]. Environmental Science and Pollution Research, 24(31): 24400-24408.
[7]	LIN M Z, CHEN H, CHEN W F, et al., 2014. Effect of single-cation doping and codoping with Mn and Fe on the photocatalytic performance of TiO₂ thin films[J]. International Journal of Hydrogen Energy, 39(36): 21500-21511.
[8]	LIU X Y, HUANG F, YU Y, et al., 2019. Ofloxacin degradation over Cu-Ce tyre carbon catalysts by the microwave assisted persulfate process[J]. Applied Catalysis B: Environmental, 253: 149-159.
[9]	LIU Y, GUO H G, ZHANG Y L, et al., 2018. Heterogeneous activation of peroxymonosulfate by sillenite Bi₂₅FeO₄₀: singlet oxygen generation and degradation for aquatic levofloxacin[J]. Chemical Engineering Journal, 343: 128-137.
[10]	LIU Z B, REN X, DUAN X Y, et al., 2022. Remediation of environmentally persistent organic pollutants (POPs) by persulfates oxidation system (PS): A review[J]. The Science of the Total Environment, 863: 160818.
[11]	MAO J, QUAN X, WANG J, et al., 2018. Enhanced heterogeneous Fenton-like activity by Cu-doped BiFeO₃ perovskite for degradation of organic pollutants[J]. Frontiers of Environmental Science & Engineering, 12(6): 1-10.
[12]	OUYANG M Y, LI X M, XU Q X, et al., 2020. Heterogeneous activation of persulfate by Ag doped BiFeO₃ composites for tetracycline degradation[J]. Journal of Colloid and Interface Science, 566: 33-45.
[13]	WANG J Q, GUO H G, LIU Y, et al., 2022. Peroxymonosulfate activation by porous BiFeO₃ for the degradation of bisphenol AF: Non-radical and radical mechanism[J]. Applied Surface Science, 507: 145097.
[14]	WANG Y, JI Q J, XU J X, et al., 2021. Activation of peroxydisulfate using N-doped carbon-encapsulated Ni species for efficient degradation of tetracycline[J]. Separation and Purification Technology, 276: 119369.
[15]	WU Y, LUO H J, JIANG X L, et al., 2014. Facile synthesis of magnetic Bi₂₅FeO₄₀/rGO catalyst with efficient photocatalytic performance for phenolic compounds under visible light[J]. Royal Society of Chemistry Advance, 5(7): 4905-4908.
[16]	ZHANG H X, CHENG S, LI B, et al., 2018. Fabrication of magnetic Co/BiFeO₃ composite and its advanced treatment of pharmaceutical waste water by activation of peroxysulphate[J]. Separation and Purification Technology, 202: 242-247.
[17]	ZOU Y B, LI W T, YANG L, et al., 2019. Activation of peroxymonosulfate by sp²-hybridized microalgae-derived carbon for ciprofloxacin degradation: Importance of pyrolysis temperature[J]. Chemical Engineering Journal, 370: 1286-1297.
[18]	董欣竹, 钱林波, 龙颖, 等, 2023. 高级氧化技术修复萘污染土壤和地下水研究进展[J]. 土壤, 55(1): 11-20.
	DONG X Z, QIAN L B, LONG Y, et al., 2023. Research progresses on advanced oxidation technologies to remediate naphthalene-contaminated soil and groundwater[J]. Soils, 55(1): 11-20.
[19]	段光相, 2023. 拜耳赤泥基催化剂制备及其高级氧化催化降解抗生素的研究[D]. 南宁: 广西大学.
	DUAN G X, 2023. Preparation of bayer red mud based catalyst and its study in advanced oxidation process of degradation of antibiotics[D]. Nanning: Guangxi University.
[20]	葛永翔, 褚衍玉, 任高峰, 等, 2021. 高海拔矿山井下环境对安全人因指标影响机理研究[J]. 中国安全生产科学技术, 17(7): 110-116.
	GE Y X, CHU Y Y, REN G F, et al., 2021. Study on influence mechanism of underground environment in high-altitude mines on safety human factor indexes[J]. China Safety Science and Technology, 17(7): 110-116.
[21]	韩瑞瑞, 郑瑾, 高春阳, 等, 2023. 碳载铁基双金属活化过硫酸盐降解有机污染物[J]. 环境科学与技术, 46(S1): 102-108.
	HAN R R, ZHENG J, GAO C Y, et al., 2023. Iron-based bimetallic activation of persulfate for degradation of organic pollutants[J]. Environmental Science & Technology, 46(S1): 102-108.
[22]	胡俊生, 李嘉宝, 王海曼, 等, 2024. 基于响应面法的微电解活化过硫酸盐降解苯酚研究[J]. 沈阳建筑大学学报(自然科学版), 40(3): 570-576.
	HU J S, LI J B, WANG H M, et al., 2024. Degradation of phenol by micro-electrolysis activated persulfate based on response surface methodology[J]. Journal of Shenyang Jianzhu University (Natural Science), 40(3): 570-576.
[23]	黄仕元, 林森焕, 董雯, 等, 2023. 锰氮共掺杂稻壳生物炭活化过二硫酸盐降解酸性橙[J]. 复合材料学报, 40(2): 1071-1084.
	HUANG S Y, LIN S H, DONG W, et al., 2023. Manganese-nitrogen co-doped rice husk biochar activated peroxydisulfate to degrade acid orange[J]. Acta Materiae Compositae Sinica, 40(2): 1071-1084.
[24]	李宗阳, 张庆福, 张团, 等, 2023. 盐水层CO₂溶解埋存潜力确定方法[J]. 油气地质与采收率, 30(2): 174-180.
	LI Z Y, ZHANG Q F, ZHANG T, et al., 2023. Method for determining potential of dissolved CO₂ storage in brine layers[J]. Petroleum Geology and Recovery Efficiency, 30(2): 174-180.
[25]	刘博, 高宁, 2023. 响应面法优化真菌CHS₃发酵产物中柴胡皂苷d的提取工艺[J]. 化学工程师, 37(12): 90-95, 100.
	LIU B, GAO N, 2023. Optimization of saikosaponin d extraction from CHS3 strain fermentation products by response surface methodology[J]. Chemical Engineer, 37(12): 90-95, 100.
[26]	刘霞, 李硕, 郑永杰, 等, 2023. Mn-Bi₂₅FeO₄₀催化活化过硫酸盐高效降解抗生素磺胺嘧啶的研究[J]. 齐齐哈尔大学学报(自然科学版), 39(2): 76-82.
	LIU X, LI S, ZHENG Y J, et al., 2023. Study on efficient degradation of sulfadiazine by Mn-Bi₂₅FeO₄₀catalytically activated persulfate[J]. Journal of Qiqihar University (Natural Science Edition), 39(2): 76-82
[27]	刘杨, 张永丽, 周鹏, 2022. 软铋矿铁酸铋活化过一硫酸盐降解环丙沙星机理及产物研究[J]. 工程科学与技术, 54(5): 203-209.
	LIU Y, ZHANG Y L, ZHOU P, 2022. Study on mechanism and products of degradation of ciprofloxacin by sillenite bismuth ferrite-activated persulfate[J]. Engineering Science and Technology, 54(5): 203-209.
[28]	马亚蒙, 2023. 三维电芬顿活化过氧乙酸去除废水中磺胺类抗生素的效能研究[D]. 南京: 南京信息工程大学.
	MA Y M, 2023. Investigation on the efficiency of 3D electro-fenton process for the removal of sulfonamide antibiotics from wastewater using peroxyacetic acid[D]. Nanjing: Nanjing University of Information Science & Technology.
[29]	欧阳磊, 丁耀彬, 朱丽华, 等, 2013. 钴掺杂铁酸铋活化过硫酸盐降解水中四溴双酚A的研究[J]. 环境科学, 34(9): 3507-3512.
	OUYANG L, DING Y B, ZHU L H, et al., 2013. Efficient Degradation of Tetrabromobisphenol A in Water by Co-doped BiFeO₃[J]. Environmental Science, 34(9): 3507-3512.
[30]	潘诗婷, 2023. MXene介导的PMS氧化体系中间态活性物种产生机制与降解有机污染物研究[D]. 东莞: 东莞理工学院.
	PAN S T, 2023. The study of intermediate active species production mechanism and organic pollutants degradation in MXene-mediated PMS oxidation system[D]. Dongguan: Dongguan University of Technology.
[31]	王晓云, 付爱民, 2024. Ag掺杂MnFe₂O₄/UV活化过硫酸盐降解废水中对硝基苯酚[J]. 环境科学学报, 44(9): 245-260.
	WANG X Y, FU A M, 2024. Ag-doped MnFe₂O₄/UV-activated persulfate degradation of p-Nitrophenol in wastewater[J]. Journal of Environmental Sciences, 44(9): 245-260.
[32]	王振宇, 2021. 铒离子掺杂铁酸铋活化过二硫酸盐降解2,4-二氯苯酚的研究[D]. 衡阳: 南华大学.
	WANG Z Y, 2021. Activation persoxodisulfate by Erbiumion-doped bismuth ferrite for Degradation of 2,4-dichlorophenol[D]. Hengyang: University of South China.
[33]	许苗, 2023. 纳米铁钴基催化剂活化过硫酸盐降解左氧氟沙星的研究[D]. 兰州: 兰州理工大学.
	XU M, 2023. Degradation of Levofloxacin by Activated Persulfate with nanometer iron cobalt based catalysts[D]. Lanzhou: Lanzhou University of Technology.
[34]	闫云涛, 张柯, 程星星, 等, 2021. Fe₃O₄@MSCe/H₂O₂多相芬顿体系的分解性能及放热规律研究[J]. 哈尔滨工业大学学报, 53(1): 147-154, 175.
	YAN Y T, ZHANG K, CHENG X X, et al., 2021. Study on degradation performance and exothermic law of Fe₃O₄@MSCe/H₂O₂multiphase Fenton system[J]. Journal of Harbin Institute of Technology, 53(1): 147-154, 175.
[35]	杨梦鑫, 王亚静, 刘文佳, 等, 2024. 生物炭活化过硫酸盐工艺去除抗生素研究进展[J]. 现代化工, 44(8): 64-68. DOI
	YANG M X, WANG Y J, LIU W J, et al., 2024. Research progress on the removal of antibiotics by biochar-activated persulfate process[J]. Modern Chemical Industry, 44(8): 64-68.
[36]	杨威, 王国相, 陈俊楠, 等, 2024. 稻壳生物炭/过硫酸盐降解水中四环素的研究[J]. 应用化工, 53(2): 341-345.
	YANG W, WANG G X, CHEN J N, et al., 2024. Degradation of tetracycline in water by biochar-based rice husk and persulfate[J]. Applied Chemical Industry, 53(2): 341-345.
[37]	岳振, 2020. 原位电芬顿法深度处理畜禽养殖废水中磺胺嘧啶研究[D]. 武汉: 武汉轻工大学.
	YUE Z, 2020. Sulfadiazine removed from livestock and poultry breeding wastewater using an in-situ Electro-Fenton process[D]. Wuhan: Wuhan Polytechnic University.
[38]	张硕, 2024. 铬渣基催化剂在过硫酸盐体系下对有机废水降解性能及机理研究[D]. 重庆: 重庆理工大学.
	ZHANG S, 2024. Degradation performance and mechanism of chromium slag-based catalysts for organic wastewater under persulfate system[D]. Chongqing: Chongqing University of Technology.
[39]	张婷婷, 未碧贵, 赵福正, 等, 2023. 碳材料活化过硫酸盐高级氧化技术降解抗生素的研究进展[J]. 山东化工, 52(23): 113-119.
	ZHANG T T, WEI B G, ZHAO F Z, et al., 2023. Degradation of antibiotics by carbon materials activated persulfate advanced oxidation process[J]. Shandong Chemical Industry, 52(23): 113-119.

Cu_x-Bi₂₅FeO₄₀活化过硫酸盐降解水中磺胺嘧啶研究

Degradation of Sulfadiazine by Cu_x-Bi₂₅FeO₄₀Activated Persulfate

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 39

相关文章 5

编辑推荐

Metrics

本文评价

[1]	赵乐依, 朱雪强, 刘健, 路平. 碳球负载纳米零价铁活化过硫酸盐降解水中恩诺沙星的性能研究[J]. 生态环境学报, 2024, 33(5): 757-770.
[2]	丛鑫, 曹平, 王晓博. 生物炭负载纳米铁活化过硫酸盐去除土壤中的五氯联苯[J]. 生态环境学报, 2024, 33(2): 282-290.
[3]	王铁铮, 瞿心悦, 刘春香, 李有志. 东江湖水质时空变化规律及其与流域土地利用的关系[J]. 生态环境学报, 2023, 32(4): 722-732.
[4]	白海锋, 王怡睿, 宋进喜, 孔飞鹤, 张雪仙, 李琦. 渭河浮游生物群落结构特征及其与环境因子的关系[J]. 生态环境学报, 2022, 31(1): 117-130.
[5]	张太平, 肖嘉慧, 胡凤洁. 生物炭固定化微生物技术在去除水中污染物的应用研究进展[J]. 生态环境学报, 2021, 30(5): 1084-1093.