多孔Ni/Co水滑石活化过硫酸盐降解磺胺甲<inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="1005-829X-2024-44-8-162/D2F9A8D5-7A74-4702-8F33-DFF12070E600-F501c.jpg"> </inline-graphic>唑研究

doi:10.19965/j.cnki.iwt.2023-0849

摘要/Abstract

摘要：

以沸石咪唑酯骨架材料（ZIFs）为模板，采用水热法合成了具有多孔结构和大比表面积的Ni/Co水滑石催化剂，表征分析了催化剂的物化性质，并以磺胺甲唑溶液为模拟废水，考察了多孔Ni/Co水滑石催化活化过硫酸盐降解水中磺胺甲唑的性能。表征结果表明，该催化剂具有纳米菱形结构，孔尺寸较大，比表面积可达187.99 m²/g。降解水中磺胺甲唑实验表明：在30 ℃，磺胺甲唑质量浓度为15 mg/L，PMS为2 g/L，Ni/Co水滑石催化剂投加量为100 mg/L的条件下，反应时间为20 min时，磺胺甲唑的去除率约100%，且重复使用4次后，磺胺甲唑的降解率仍大于90%，表现出较好的稳定性和重复使用性能。猝灭及电子顺磁共振实验表明，催化降解过程中SO₄ ^•-、·OH和¹O₂均参与了反应。通过对多孔Ni/Co水滑石反应前后表面元素价态的分析，发现催化剂表面的Co²⁺/Co³⁺以及Ni²⁺/Ni³⁺的循环有效活化了PMS并促进活性氧化物种的生成，从而提升了过硫酸盐降解磺胺甲唑的性能。

关键词: 水滑石, 沸石咪唑酯骨架材料, 过硫酸盐, 降解, 磺胺甲唑

Abstract:

In this paper,nano-Ni/Co hydrotalcite catalysts were synthesized by hydrothermal method using zeolite imidazolate framework materials(ZIFs) as templates, and the physico chemical properties of the catalysts were characterized. With sulfamethoxazole solution as simulated wastewater, the catalytic performance of nano-Ni/Co hydrotalcite to degrade sulfamethoxazole in water via persulfate activation was investigated. Characterization results showed that the catalyst had a nano-rhomboid structure with large pore size and a specific surface area of 187.99 m²/g. The degradation experiment results showed that the removal rate of sulfamethoxazole was about 100% in 20 min, under the conditions of 30 ℃, the concentration of sulfamethoxazole as 15 mg/L, the amount of PMS as 2 g/L, and the amount of Ni/Co hydrotalcite catalyst as 100 mg/L. After reuse of 4 times, the degradation rate of sulfamethoxazole was still greater than 90%, showing its good stability and reusability. Quenching experiments and electron paramagnetic resonance analysis showed that SO₄ ^•-, ·OH and ¹O₂ participated in the degradation reaction. During the reaction process, the redox cycle of Co²⁺/Co³⁺ and Ni²⁺/Ni³⁺ effectively activated PMS and promoted the generation of active oxide species, which improved the performance of the catalyst for the degradation of sulfamethoxazole.

Key words: hydrotalcite, zeolitic imidazolate frameworks, peroxymonosulfate, degradation, sulfamethoxazole

中图分类号:

X703.1

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.

Lei ZHANG, Jin ZHANG, Xinlong YAN. Synthesis of porous Ni/Co LDHs and its degradation behavior for sulfamethoxazole via peroxymonosulfate activation[J]. Industrial Water Treatment, 2024, 44(8): 162-170.

https://www.iwt.cn/CN/Y2024/V44/I8/162

图/表 13

图1 ZIF-67、Co-NC和Ni/Co-NC LDH的XRD

Fig.1 XRD of ZIF-67，Co-NC and Ni/Co-NC LDH

图2 Co-NC（a~b）和Ni/Co-NC LDH（c~e）的SEM，以及Ni/Co-NC LDH的相应元素分布（f~h）

Fig.2 SEM images of Co-NC（a-b） and Ni/Co-NC LDH（c-e），and the corresponding elemental distribution of Ni/Co-NC LDH（f-h）

图3 ZIF-67、Co-NC和Ni/Co-NC LDH的红外光谱

Fig.3 FT-IR spectrum of ZIF-67，Co-NC and Ni/Co-NC LDH

图4 Co-NC和Ni/Co-NC LDH的氮气吸附-脱附曲线（a）和孔径分布（b）

Fig.4 Nitrogen sorption isotherms（a） and pore size distributions（b） of Co-NC and Ni/Co-NC LDH

表1 Co-NC和Ni/Co-NC LDH的孔结构性质

Table 1 Textural properties of Co-NC and Ni/Co-NC LDH

样品	比表面积/（m²·g^-1）	总孔容/（cm³·g^-1）	微孔孔容/（cm³·g^-1）	介孔孔容/（cm³·g^-1）	平均孔径/nm
Co-NC	354.1	0.21	0.15	0.03	2.3
Ni/Co-NC LDH	187.9	0.24	0.08	0.16	5.1

图5 Co-NC和Ni/Co-NC LDH的XPS光谱

Fig.5 XPS spectra for Co-NC and Ni/Co-NC LDH

图6 SMX在不同催化剂体系中的降解效率

Fig.6 Degradation efficiencies of SMX in different catalyst systems

图7 催化剂投加量（a）和PMS浓度（b）对SMX降解的影响

Fig.7 Effect of catalyst dosage （a） and PMS concentration （b） on degradation of SMX

图8 pH对SMX降解的影响

Fig.8 Effect of pH on the degradation of SMX

图9 不同猝灭剂对Ni/Co-NC LDH活化PMS降解SMX的影响

Fig.9 Effect of different quenching agents on Ni/Co-NC LDH activated PMS to degrade SMX

图10 Ni/Co-NC LDH/PMS体系的EPR

Fig.10 EPR of the Ni/Co-NC LDH/PMS systems

图11 SMX降解实验前后Ni/Co-NC LDH的XPS

Fig.11 XPS spectra of Ni/Co-NC LDH before and after SMX degradation

图12 Ni/Co-NC LDH/PMS体系降解SMX的循环实验结果

Fig.12 Cyclic experimental results of degradation of SMX by Ni/Co-NC LDH/PMS system

参考文献 28

1	KAIRIGO P， NGUMBA E， SUNDBERG L R，et al. Occurrence of antibiotics and risk of antibiotic resistance evolution in selected Kenyan wastewaters，surface waters and sediments［J］. Science of the Total Environment，2020，720：137580. doi:10.1016/j.scitotenv.2020.137580
2	GE Linke， ZHANG Peng， HALSALL C，et al. The importance of reactive oxygen species on the aqueous phototransformation of sulfonamide antibiotics：Kinetics，pathways，and comparisons with direct photolysis［J］. Water Research，2019，149：243-250. doi:10.1016/j.watres.2018.11.009
3	林靖钧，李瑞雪，林华，等. 我国水产养殖水体中抗生素的污染特征［J］. 净水技术，2022，41（3）：12-19.
	LIN Jingjun， LI Ruixue， LIN Hua，et al. Pollution characteristics of antibiotics in aquaculture water at home［J］. Water Purification Technology，2022，41（3）：12-19.
4	胡伟，牛耀岚，董堃，等. 甘蔗渣生物炭对典型抗生素的去除机理研究［J］. 水处理技术，2022，48（11）：52-56.
	HU Wei， NIU Yaolan， DONG Kun，et al. Study on removal mechanism of typical antibiotics by bagasse biochar［J］. Technology of Water Treatment，2022，48（11）：52-56.
5	白杨. 污水厂中磺胺类抗生素的去除效率与残留特征［D］. 哈尔滨：哈尔滨工程大学，2012.
	BAI Yang. Removal efficiency and residue characteristics of sulfonamides in sewage plants［D］. Harbin：Harbin Engineering University，2012.
6	MARTINI J， ORGE C A， FARIA J L，et al. Sulfamethoxazole degradation by combination of advanced oxidation processes［J］. Journal of Environmental Chemical Engineering，2018，6（4）：4054-4060. doi:10.1016/j.jece.2018.05.047
7	LI Chenxu， WU Jiaen， PENG Wei，et al. Peroxymonosulfate activation for efficient sulfamethoxazole degradation by Fe₃O₄/β-FeOOH nanocomposites：Coexistence of radical and non-radical reactions［J］. Chemical Engineering Journal，2019，356：904-914. doi:10.1016/j.cej.2018.09.064
8	陈晴空，雷翼妃，陈治君，等. 碳化ZIF-67催化过硫酸盐降解水中的甲基橙［J］. 工业水处理，2023，43（8）：89-96. doi:10.19965/j.cnki.iwt.2022-0855
	CHEN Qingkong， LEI Yifei， CHEN Zhijun，et al. Degradation of methyl orange in water by persulfate catalyzed with carbonized ZIF-67［J］. Industrial Water Treatment，2023，43（8）：89-96. doi:10.19965/j.cnki.iwt.2022-0855
9	XIAO Ruiyang， LUO Zonghao， WEI Zongsu，et al. Activation of peroxymonosulfate/persulfate by nanomaterials for sulfate radical-based advanced oxidation technologies［J］. Current Opinion in Chemical Engineering，2018，19：51-58. doi:10.1016/j.coche.2017.12.005
10	BODHANKAR P M， SARAWADE P B， SINGH G，et al. Recent advances in highly active nanostructured NiFe LDH catalyst for electrochemical water splitting［J］. Journal of Materials Chemistry A，2021，9（6）：3180-3208. doi:10.1039/d0ta10712c
11	AHMED A A ALI， TALIB Z A， HUSSEIN M Z BIN，et al. Zn-Al layered double hydroxide prepared at different molar ratios：Preparation，characterization，optical and dielectric properties［J］. Journal of Solid State Chemistry，2012，191：271-278. doi:10.1016/j.jssc.2012.03.013
12	LI Xu， LIU Shuangyi， BAI Sihan，et al. Zeolitic-imidazolate framework derived Ni-Co layered double hydroxide hollow microspheres with enhanced pseudocapacitive properties for hybrid supercapacitors［J］. Journal of Materials Chemistry C，2022，10（16）：6348-6357. doi:10.1039/d1tc05792h
13	JIANG Tingting， WANG Xi， CHEN Jiazhi，et al. Hierarchical Ni/Co-LDHs catalyst for catalytic oxidation of indoor formaldehyde at ambient temperature［J］. Journal of Materials Science：Materials in Electronics，2020，31（4）：3500-3509. doi:10.1007/s10854-020-02898-7
14	QIAN Junfeng， SUN Fuan， QIN Lizhen. Hydrothermal synthesis of zeolitic imidazolate framework-67（ZIF-67） nanocrystals［J］. Materials Letters，2012，82：220-223. doi:10.1016/j.matlet.2012.05.077
15	CHEN Yuzhen， WANG Chengming， WU Zhenyu，et al. From bimetallic metal-organic framework to porous carbon：High surface area and multicomponent active dopants for excellent electrocatalysis［J］. Advanced Materials，2015，27（34）：5010-5016. doi:10.1002/adma.201502315
16	MA Wenjie， WANG Na， FAN Yanan，et al. Non-radical-dominated catalytic degradation of bisphenol A by ZIF-67 derived nitrogen-doped carbon nanotubes frameworks in the presence of peroxymonosulfate［J］. Chemical Engineering Journal，2018，336：721-731. doi:10.1016/j.cej.2017.11.164
17	HUANG Cheng， SU Xiaoyan， GU Xiangyu，et al. Bimetallic oxide nanoparticles confined in ZIF-67-derived carbon for highly selective oxidation of saturated C-H bond in alkyl arenes［J］. Applied Organometallic Chemistry，2021，35（1）：e6047. doi:10.1002/aoc.6047
18	刘明明，吕文苗，史秀锋，等. 不同方法合成的沸石咪唑酯骨架结构材料（ZIF-8）的表征和催化性能［J］. 无机化学学报，2014，30（3）：579-584. doi:10.11862/CJIC.2014.009
	LIU Mingming， Wenmiao LÜ， SHI Xiufeng，et al. Characterization and catalytic performence of zeolitic imidazolate framework-8（ZIF-8） synthesized by different methods［J］. Chinese Journal of Inorganic Chemistry，2014，30（3）：579-584. doi:10.11862/CJIC.2014.009
19	NAGARAJU G， CHANDRA SEKHAR S， KRISHNA BHARAT L，et al. Wearable fabrics with self-branched bimetallic layered double hydroxide coaxial nanostructures for hybrid supercapacitors［J］. ACS Nano，2017，11（11）：10860-10874. doi:10.1021/acsnano.7b04368
20	HU Haojun， LIU Jiyan， XU Zhihua，et al. Hierarchical porous Ni/Co-LDH hollow dodecahedron with excellent adsorption property for Congo red and Cr（Ⅵ） ions［J］. Applied Surface Science，2019，478：981-990. doi:10.1016/j.apsusc.2019.02.008
21	CHEN Liwei， YANG Shengjiong， ZUO Xu，et al. Biochar modification significantly promotes the activity of Co₃O₄ towards heterogeneous activation of peroxymonosulfate［J］. Chemical Engineering Journal，2018，354：856-865. doi:10.1016/j.cej.2018.08.098
22	TAHIR M U， ARSHAD H， ZHANG Heng，et al. Room temperature and aqueous synthesis of bimetallic ZIF derived CoNi layered double hydroxides and their applications in asymmetric supercapacitors［J］. Journal of Colloid and Interface Science，2020，579：195-204. doi:10.1016/j.jcis.2020.06.050
23	HE Yongli， ZHANG Jiali， ZHOU Hongyu，et al. Synergistic multiple active species for the degradation of sulfamethoxazole by peroxymonosulfate in the presence of CuO@FeO _x @Fe⁰ ［J］. Chemical Engineering Journal，2020，380：122568. doi:10.1016/j.cej.2019.122568
24	JIA Muhan， FAN Yan， SUN Zhirong，et al. ZrO₂ supported perovskite activation of peroxymonosulfate for sulfamethoxazole removal from aqueous solution［J］. Chemosphere，2022，298：134339. doi:10.1016/j.chemosphere.2022.134339
25	HUANG Wen， TANG Yaxin， ZHANG Xueping，et al. nZVI-biochar derived from Fe₃O₄-loaded rabbit manure for activation of peroxymonosulfate to degrade sulfamethoxazole［J］. Journal of Water Process Engineering，2022，45：102470. doi:10.1016/j.jwpe.2021.102470
26	苏冰琴，温宇涛，林昱廷，等. 活性碳纤维-过硫酸盐体系处理焦化废水生化出水的实验研究［J］. 环境科学学报，2022，42（7）：182-195.
	SU Bingqin， WEN Yutao， LIN Yuting，et al. Advanced treatment of bio-treated coking wastewater with peroxymonosulfate activated by activated carbon fiber system［J］. Acta Scientiae Circumstantiae，2022，42（7）：182-195.
27	DURAIRAJ A， SAM D K， SAKTHIVEL T，et al. Synthesis of bi-functional Ni/Co phosphate nanocomposites for Peroxymonosulphate activation and supercapacitor electrode［J］. Journal of Environmental Chemical Engineering，2021，9（6）：106426. doi:10.1016/j.jece.2021.106426
28	LIU Li， LI Yunong， LI Wei，et al. The efficient degradation of sulfisoxazole by singlet oxygen（¹O₂） derived from activated peroxymonosulfate（PMS） with Co₃O₄-SnO₂/RSBC［J］. Environmental Research，2020，187：109665. doi:10.1016/j.envres.2020.109665

[1]	徐浩, 张凡, 于鑫, 陈红, 薛罡. 铁铜微电解-Fenton联合工艺去除磺胺甲唑和卡马西平[J]. 工业水处理, 2025, 45(3): 55-64.
[2]	张强, 彭宇华, 张静, 马军. 碱性水热法高效降解全氟/多氟烷基化合物[J]. 工业水处理, 2025, 45(3): 1-9.
[3]	韩雨璇, 倪志娇, 卢洪伟. 添加剂对DBD处理亚甲基蓝模拟废水的影响[J]. 工业水处理, 2025, 45(3): 165-174.
[4]	傅翔宇, 李亚峰, 刘奕含, 崔可清, 王玲萍. 磷酸三丁酯改性生物炭活化PMS降解双酚A的效能[J]. 工业水处理, 2025, 45(1): 87-93.
[5]	郑国庆, 黄煜坤, 韩要丛, 薛兴勇, 卢彦越, 蓝丽红, 陈贞南. 锰渣活化过一硫酸盐降解罗丹明B[J]. 工业水处理, 2025, 45(1): 79-86.
[6]	周朝云, 令玉林, 蒋文雪, 周建红. WO₃/rGO/BiOBr的制备及其光催化降解环丙沙星废水的性能研究[J]. 工业水处理, 2025, 45(1): 73-78.
[7]	徐玲莉, 刘玉香, 董静, 任莉, 王文君, 袁可. 苯酚高效降解菌群的群落结构及其代谢产物研究[J]. 工业水处理, 2024, 44(9): 85-90.
[8]	郭紫瑞, 李红艳, 张峰, 崔佳丽, 杨群, 李赟. Fe₂O₃-CuO/rCG催化降解水中苯并三氮唑的效能与机理[J]. 工业水处理, 2024, 44(9): 118-126.
[9]	卫昆, 赵丽嫦, 陈慕羽, 黄皖唐, 方嘉声, 唐少宇. 水环境中溴系阻燃剂处理技术及毒理效应研究进展[J]. 工业水处理, 2024, 44(9): 9-22.
[10]	王渤, 张立杰, 陈俊任, 任子安, 齐悦君. 微藻处理含抗生素类废水研究进展[J]. 工业水处理, 2024, 44(8): 44-52.
[11]	赵杰, 吴俊峰, 窦艳艳, VIKTOROVICH Fedorov Svyatoslav, 王现丽, 刘彪, 朱新锋, 毛艳丽, 高宏斌. 单原子活化过硫酸盐降解有机污染物研究进展[J]. 工业水处理, 2024, 44(7): 38-46.
[12]	柴瑾, 白雪, 张祉瑶, 胡敏, 石娟, 金鹏康. 顺丁烯二酸活化过硫酸盐降解染料有机物研究[J]. 工业水处理, 2024, 44(6): 151-157.
[13]	商伟伟, 杨焱, 沈芸, 赵世荣, 薛罡, 钱雅洁. 高铁酸盐耦合过氧乙酸深度处理水中甲硝唑的特性研究[J]. 工业水处理, 2024, 44(5): 111-119.
[14]	李泽乙, 廖常盛, 柴云, 王庆宏, 詹亚力, 陈春茂, 陈发源. 焦化废水生化尾水特征及其深度处理技术进展[J]. 工业水处理, 2024, 44(3): 10-23.
[15]	张静, 张彦平, 裴佳华, 贾小赛, 李一兵, 吕宁. 铁基污泥炭活化过硫酸盐调理剩余污泥脱水的效能和机理研究[J]. 工业水处理, 2024, 44(3): 142-151.

选择文件类型/文献管理软件名称

选择包含的内容

多孔Ni/Co水滑石活化过硫酸盐降解磺胺甲唑研究

Synthesis of porous Ni/Co LDHs and its degradation behavior for sulfamethoxazole via peroxymonosulfate activation

RichHTML

PDF

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 28

相关文章 15

编辑推荐

Metrics

本文评价

模态框（Modal）标题

选择文件类型/文献管理软件名称

选择包含的内容

多孔Ni/Co水滑石活化过硫酸盐降解磺胺甲 唑研究

Synthesis of porous Ni/Co LDHs and its degradation behavior for sulfamethoxazole via peroxymonosulfate activation

RichHTML

PDF

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 28

相关文章 15

编辑推荐

Metrics

本文评价

多孔Ni/Co水滑石活化过硫酸盐降解磺胺甲唑研究