羟胺/磁性铜铁氧体活化过硫酸盐高效降解磺胺甲 唑

doi:10.19965/j.cnki.iwt.2024-0612

摘要/Abstract

摘要：

通过溶胶-凝胶燃烧法制备了以CuFe₂O₄为主要成分、具有（311）晶面的磁性铜铁氧体材料（CFO），在羟胺（HA）辅助下该催化材料可高效活化过硫酸盐（PDS）降解磺胺甲唑（SMX）。实验结果表明，pH在5~9的范围内，SMX在CFO/PDS/HA体系中60 min的降解率均可达80%以上，HA、PDS和CFO在适当的投加浓度范围内均与SMX降解速率呈现正相关性。基于阿伦尼乌斯方程的温度-降解速率拟合曲线表明，该催化降解反应受限于化学反应速率而非界面传质。通过进一步的铜铁位点角色分析，推测HA促进了CFO表面的Cu（Ⅰ）/Cu（Ⅱ）和Fe（Ⅱ）/Fe（Ⅲ）循环，从而支持了PDS的非均相高效催化分解；自由基鉴定和猝灭实验则表明，¹O₂和·OH为SMX的去除做出了主要贡献。在常见阴离子共存下CFO/PDS/HA体系也具有较好的表现，其中NO₃ ^-与SO₄ ^2-对CFO/PDS/HA体系中SMX降解的影响较小，Cl^-、Br^-和HCO₃ ^-在中低浓度下可显著加速SMX降解。

关键词: 铜铁氧体, 过硫酸盐, 催化氧化, 磺胺甲唑

Abstract:

Magnetic copper ferrite(CFO) mainly consisting of CuFe₂O₄ and with(311) crystal face was synthesized through sol-gel combustion method. It could efficiently activate persulfate(PDS) to degrade sulfamethoxazole(SMX) at the presence of hydroxylamine(HA). Results showed that the removal rate of SMX could be above 80% in the CFO/PDS/HA system with pH from 5-9. At rational concentration scope, the dosages of HA, PDS and CFO were positively related to the removal efficiency of SMX, respectively. According to the linearly fitting of temperature versus degradation rate based on Arrhenius equation, it could be confirmed that the catalytic reaction for SMX degradation was limited by chemical reaction rate instead of interfacial mass transfer. Further analysis for the role of copper and iron site indicated that HA promoted the Cu(Ⅰ)/Cu(Ⅱ) and Fe(Ⅱ)/Fe(Ⅲ) cycle on CFO surface, which supported the heterogeneously effective catalysis of PDS. The identification of radicals and quenching experiments indicated that the main contribution to the removal of SMX was made by ¹O₂ and ·OH. Even with the coexistence of common anions, the CFO/PDS/HA system also exhibited good performance. Negligible effect was found with NO₃ ^- or SO₄ ^2- while Cl^- and Br^- at mediate concentration would significantly accelerate the degradation of SMX.

Key words: copper ferrite, persulfate, catalytic oxidation, sulfamethoxazole

中图分类号:

X703.1

邹磊, 向威, 王怡帆, 周涛, 马凤娟, 刘向荣. 羟胺/磁性铜铁氧体活化过硫酸盐高效降解磺胺甲唑[J]. 工业水处理, 2025, 45(8): 43-52.

Lei ZOU, Wei XIANG, Yifan WANG, Tao ZHOU, Fengjuan MA, Xiangrong LIU. Efficient degradation of sulfamethoxazole via the activation of persulfate by hydroxylamine/magnetic copper ferrite[J]. Industrial Water Treatment, 2025, 45(8): 43-52.

https://www.iwt.cn/CN/Y2025/V45/I8/43

图/表 13

图1 CFO的SEM（a）、TEM（b）、HR-TEM（c）和FFT（d）表征谱图

Fig.1 SEM（a），TEM（b），HR-TEM（c） images and FFT characterization（d） of CFO

图2 CFO的XRD谱图（a）和VSM曲线（b）

Fig.2 XRD pattern（a） and VSM curve（b） of CFO

图3 不同体系中SMX的降解曲线

Fig.3 Comparative degradation of SMX in different systems

图4 pH（a）、HA投加量（b）、PDS投加量（c）和CFO投加量（d）对SMX降解的影响

Fig.4 Effect of pH（a），HA dosage（b），PDS dosage（c） and CFO dosage（d） on the degradation of SMX

图5 温度对SMX降解的影响（a）及阿伦尼乌斯公式线性拟合（b）

Fig.5 Effect of temperature on SMX degradation（a） and the linear fitting according to Arrhenius equation（b）

图6 不同催化剂的催化降解性能

Fig. 6 Comparative performance of different catalysts

图7 2，2-联吡啶和新铜试剂对SMX降解效果的抑制作用

Fig.7 The inhibition effect of 2，2-bipyridine and neocuproine on SMX degradation

图8 添加联吡啶和新铜试剂时CFO溶出的铁和铜浓度

Fig.8 Iron and copper leaching from CFO with the addition of 2，2-bipyridine and neocuproine

图9 EPR检测谱图

Fig.9 EPR spectra in the CFO/PDS/HA system

图10 自由基猝灭试验

Fig.10 Quenching experiments of radicals

图11 SMX在CFO/PDS/HA体系中的降解路径

Fig.11 The degradation pathway of SMX in the CFO/PDS/HA system

图12 常见阴离子对CFO/PDS/HA体系中SMX降解的影响

Fig.12 The influence of common anions on the degradation of SMX in the CFO/PDS/HA system

图13 HCO₃ ^-对CFO/PDS/HA体系中SMX降解的影响

Fig. 13 The influence of HCO₃ ^- on the degradation of SMX in the CFO/PDS/HA system

参考文献 30

[1]	GUO Xu， ONG W M， ZHAO Heping，et al. Enzyme-induced reactive oxygen species trigger oxidative degradation of sulfamethoxazole within a methanotrophic biofilm［J］. Water Research，2024，253：121330. doi:10.1016/j.watres.2024.121330
[2]	DING Shiyuan， NIU Junfeng， BAO Yueping，et al. Evidence of superoxide radical contribution to demineralization of sulfamethoxazole by visible-light-driven Bi₂O₃/Bi₂O₂CO₃/Sr₆Bi₂O₉ photocatalyst［J］.Journal of Hazardous Materials，2013，262：812-818. doi:10.1016/j.jhazmat.2013.09.048
[3]	GANIYU S O， SABLE S， GAMAL EL-DIN M. Advanced oxidation processes for the degradation of dissolved organics in produced water：A review of process performance，degradation kinetics and pathway［J］. Chemical Engineering Journal，2022，429：132492. doi:10.1016/j.cej.2021.132492
[4]	MA Shouchun， YANG Dong， GUAN Yina，et al. Maximally exploiting active sites on yolk@shell nanoreactor：Nearly 100% PMS activation efficiency and outstanding performance over full pH range in Fenton-like reaction［J］. Applied Catalysis B：Environmental，2022，316：121594. doi:10.1016/j.apcatb.2022.121594
[5]	LI Yangju， DONG Haoran， LI Long，et al. Recent advances in waste water treatment through transition metal sulfides-based advanced oxidation processes［J］. Water Research，2021，192：116850. doi:10.1016/j.watres.2021.116850
[6]	CHENG Minxian， MA Rui， CHAI Guodong，et al. Nitrogen-doped carbonized polyaniline （N-CPANI） for peroxydisulfate （PDS） activation towards efficient degradation of doxycycline （DOX） via the non-radical pathway dominated by electron transfer［J］. Chemical Engineering Journal，2023，453：139810. doi:10.1016/j.cej.2022.139810
[7]	ZHANG Heng， JI Fangzhou， ZHANG Yunhong，et al. Catalytic ozonation of N，N-dimethylacetamide （DMAC） in aqueous solution using nanoscaled magnetic CuFe₂O₄ ［J］. Separation and Purification Technology，2018，193：368-377. doi:10.1016/j.seppur.2017.10.028
[8]	LI Jun， REN Yi， JI Fangzhou，et al. Heterogeneous catalytic oxidation for the degradation of p-nitrophenol in aqueous solution by persulfate activated with CuFe₂O₄ magnetic nano-particles［J］. Chemical Engineering Journal，2017，324：63-73. doi:10.1016/j.cej.2017.04.104
[9]	YAN Jianfei， PENG Jiali， LAI Leiduo，et al. Activation CuFe₂O₄ by hydroxylamine for oxidation of antibiotic sulfamethoxazole［J］. Environmental Science & Technology，2018，52（24）：14302-14310. doi:10.1021/acs.est.8b03340
[10]	XIANG Wei， ZHOU Tao， WANG Yifan，et al. 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. doi:10.1016/j.watres.2019.01.024
[11]	XIANG Wei， HUANG Mingjie， WU Xiaohui，et al. Amplification effects of magnetic field on hydroxylamine-promoted ZVI/H₂O₂ near-neutral Fenton like system［J］. Chinese Chemical Letters，2022，33（3）：1275-1278. doi:10.1016/j.cclet.2021.07.072
[12]	XIANG Wei， HUANG Mingjie， WANG Yifan，et al. New insight in the O₂ activation by nano Fe/Cu bimetals：The synergistic role of Cu（0） and Fe（Ⅱ）［J］. Chinese Chemical Letters，2020，31（10）：2831-2834. doi:10.1016/j.cclet.2020.08.006
[13]	LEE H J， KIM H E， LEE Changha. Combination of cupric ion with hydroxylamine and hydrogen peroxide for the control of bacterial biofilms on RO membranes［J］. Water Research，2017，110：83-90. doi:10.1016/j.watres.2016.12.014
[14]	HOU Xiaojing， HUANG Xiaopeng， JIA Falong，et al. Hydroxylamine promoted goethite surface Fenton degradation of organic pollutants［J］.Environmental Science & Technology，2017，51（9）：5118-5126. doi:10.1021/acs.est.6b05906
[15]	OH D， LEE C S， KANG Y G，et al. Hydroxylamine-assisted peroxymonosulfate activation using cobalt ferrite for sulfamethoxazole degradation［J］. Chemical Engineering Journal，2020，386：123751. doi:10.1016/j.cej.2019.123751
[16]	XIANG Wei， CHEN Hao， ZHONG Zhenxing，et al. Efficient degradation of carbamazepine in a neutral sonochemical FeS/persulfate system based on the enhanced heterogeneous-homogeneous sulfur-iron cycle［J］. Separation and Purification Technology，2022，282：120041. doi:10.1016/j.seppur.2021.120041
[17]	WANG Bingyu， LI Qiaoqiao， Ying LÜ，et al. Insights into the mechanism of peroxydisulfate activated by magnetic spinel CuFe₂O₄/SBC as a heterogeneous catalyst for bisphenol S degradation［J］. Chemical Engineering Journal，2021，416：129162. doi:10.1016/j.cej.2021.129162
[18]	XIANG Wei， ZHANG Beiping， ZHOU Tao，et al. An insight in magnetic field enhanced zero-valent iron/H₂O₂ Fenton-like systems：Critical role and evolution of the pristine iron oxides layer［J］. Scientific Reports，2016，6：24094. doi:10.1038/srep24094
[19]	SU Chunming， PULS R W. Kinetics of trichloroethene reduction by zerovalent iron and tin： pretreatment effect，apparent activation energy，and intermediate products［J］. Environmental Science & Technology，1999，33（1）：163-168. doi:10.1021/es980481a
[20]	REN Yueming， LIN Lingqiang， MA Jun，et al. Sulfate radicals induced from peroxymonosulfate by magnetic ferrospinel MFe₂O₄ （M=Co，Cu，Mn，and Zn） as heterogeneous catalysts in the water［J］. Applied Catalysis B：Environmental，2015，165：572-578. doi:10.1016/j.apcatb.2014.10.051
[21]	张磊，张进，闫新龙. 多孔Ni/Co水滑石活化过硫酸盐降解磺胺甲唑研究［J］. 工业水处理，2024，44（8）：162-170.
	ZHANG Lei， ZHANG Jin， YAN Xinlong. Synthesis of porous Ni/Co LDHs and its degradation behavior for sulfamethoxazole via peroxymonosulfate activation［J］. Industrial Water Treatment，2024，44（8）：162-170.
[22]	LI Meng， ZHANG Hongguo， CHENG Jiliang，et al. Unveiling the decomposing and mineralizing mechanism of novel perfluoroalkyl acids via hydroxyl radical dominated electrochemical oxidation［J］.Applied Catalysis B：Environment and Energy，2024，351：123983. doi:10.1016/j.apcatb.2024.123983
[23]	张驰，魏佳华，侯雪，等. CoFe₂O₄/MoS₂的制备及活化PMS降解四环素［J］. 工业水处理，2025，45（6）：194-201.
	ZHANG Chi， WEI Jiahua， HOU Xue，et al. Preparation of CoFe₂O₄/MoS₂ and activation of PMS for tetracycline degradation［J］. Industrial Water Treatment，2025，45（6）：194-201.
[24]	SUN Chen， WANG Huan， JIANG Tao，et al. Surface defect and carbonyl engineering of CNTs via oxygen-plasma etching：Oriented production of singlet oxygen from peroxymonosulfate activation［J］.Separation and Purification Technology，2024，337：126454. doi:10.1016/j.seppur.2024.126454
[25]	LEE H， LEE H J， SEO J，et al. Activation of oxygen and hydrogen peroxide by copper（Ⅱ） coupled with hydroxylamine for oxidation of organic contaminants［J］. Environmental Science & Technology，2016，50（15）：8231-8238. doi:10.1021/acs.est.6b02067
[26]	ZHOU Tao， ZOU Xiaoli， MAO Juan，et al. Decomposition of sulfadiazine in a sonochemical Fe⁰-catalyzed persulfate system：Parameters optimizing and interferences of wastewater matrix［J］. Applied Catalysis B：Environmental，2016，185：31-41. doi:10.1016/j.apcatb.2015.12.004
[27]	QIN Cheng， QI Yumeng， TENG Xiaolei，et al. Degradation of bisphonel AF （BPAF） by zero-valent iron activated persulfate：Kinetics，mechanisms，theoretical calculations，and effect of co-existing chloride［J］. Chemosphere，2023，316：137774. doi:10.1016/j.chemosphere.2023.137774
[28]	KIM C， THAO T T， KIM J H，et al. Effects of the formation of reactive chlorine species on oxidation process using persulfate and nano zero-valent iron［J］. Chemosphere，2020，250：126266.
[29]	PENG Jianbiao， SHI Huanhuan， LI Jianhua，et al. Bicarbonate enhanced removal of triclosan by copper（Ⅱ） catalyzed Fenton-like reaction in aqueous solution［J］. Chemical Engineering Journal，2016，306：484-491. doi:10.1016/j.cej.2016.07.088
[30]	LI Jiawei， LIU Zonghao， ZHAO Yan，et al. Heat enhanced bisphenol AF degradation in CoFe₂O₄@BC activated peroxymonosulfate process：Mechanism and the role of inorganic anions［J］. Separation and Purification Technology，2024，342：126968. doi:10.1016/j.seppur.2024.126968

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