ZnO促进多级孔ZIF-8衍生Co-Ni-N-C活化PMS降解水中左氧氟沙星

doi:10.16085/j.issn.1000-6613.2024-0357

摘要/Abstract

摘要：

ZIF-8（zeolitic imidazolate framework-8）作为一种典型的微孔材料，孔结构单一，金属负载量有限，影响其催化降解性能。添加ZnO作为模板可以有效调节ZIF-8的孔径大小和孔结构，同时具有大比表面积、高金属负载量以及丰富的孔道结构等特点。本文通过采用SEM、ICP-OES和BET等表征手段对材料的形貌结构、化学成分以及双金属负载量进行了详细分析。表征测试结果显示，加入ZnO模板后衍生得到的多级孔（微/介孔）Co-Ni-N-C材料中，双金属元素呈现高度分散的状态，不易发生团聚，并含有丰富的活性位点。降解实验研究结果表明，在Co-Ni-N-C及过氧单硫酸盐（PMS）投加量为0.30g/L、pH=9的条件下，在t=30min时对左氧氟沙星（LEV）的降解率最高可达到97.02%。在Co-Ni-N-C/PMS催化体系中，产生的羟基自由基（·OH）、硫酸盐自由基（ ^· SO₄^-）、超氧自由基（·O₂^–）和单线态氧（¹O₂）等活性物种与水中的LEV发生化学反应，导致LEV的分解或转化为其他物质，使其成为较小的分子或无害的化合物。

关键词: 沸石咪唑框架-8, ZnO模板, 过氧单硫酸盐, 多级孔结构, 左氧氟沙星

Abstract:

As a typical microporous material, ZIF-8 (zeolitic imidazolate framework-8) has a single pore structure and limited metal loading, which affects its catalytic degradation performance. The addition of ZnO as a template can effectively adjust the pore size and pore structure of ZIF-8, and has the characteristics of large specific surface area, high metal loading and rich pore structure. The morphology, chemical composition and bimetallic loading of the materials were analyzed in detail by means of SEM, ICP-OES and BET. The characterization test results showed that in the hierarchical porous (micro/mesoporous) Co-Ni-N-C material derived from the addition of ZnO template, the double metal elements were highly dispersed, not easy to agglomerate, and contained abundant active sites. The results of degradation experiments indicated that the degradation rate of levofloxacin (LEV) could reach 97.02% at t=30min when the dosage of Co-Ni-N-C and peroxonosulfate (PMS) was 0.30g/L and pH=9. In the Co-Ni-N-C/PMS catalytic system, the active species such as hydroxyl radical (·OH), sulfate radical (·SO₄^-), superoxide radical (·O₂^–) and singlet oxygen (¹O₂) produced by the catalytic system reacted with LEV in water, resulting in the decomposition or conversion of LEV into other substances, making it a smaller molecule or harmless compound.

Key words: ZIF-8, ZnO template, peroxonosulfate, multi stage pore structure, levofloxacin

中图分类号:

景凌云, 刘莎莎, 张泽强, 刘光龙, 蒋莉, 孙志丽, 胡叶强, 郝鹏波, 郑银琴, 杨辉. ZnO促进多级孔ZIF-8衍生Co-Ni-N-C活化PMS降解水中左氧氟沙星[J]. 化工进展, 2025, 44(3): 1683-1694.

JING Lingyun, LIU Shasha, ZHANG Zeqiang, LIU Guanglong, JIANG Li, SUN Zhili, HU Yeqiang, HAO Pengbo, ZHENG Yinqin, YANG Hui. ZnO promotes the degradation of levofloxacin in water by hierarchical porous ZIF-8 derived Co-Ni-N-C activated PMS[J]. Chemical Industry and Engineering Progress, 2025, 44(3): 1683-1694.

图/表 17

参考文献 29

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样品	取样质量/g	定容体积/mL	稀释系数	所测元素	质量分数/%
Co-Ni-N-C (含ZnO)	0.042	25	1	Co	0.165
Co-Ni-N-C (无ZnO)	0.042	25	1	Co	0.028
Co-Ni-N-C (含ZnO)	0.042	25	1	Ni	0.217
Co-Ni-N-C (无ZnO)	0.042	25	1	Ni	0.015

样品	取样质量/g	定容体积/mL	稀释系数	所测元素	质量分数/%
Co-Ni-N-C (含ZnO)	0.042	25	1	Co	0.165
Co-Ni-N-C (无ZnO)	0.042	25	1	Co	0.028
Co-Ni-N-C (含ZnO)	0.042	25	1	Ni	0.217
Co-Ni-N-C (无ZnO)	0.042	25	1	Ni	0.015

样品	微孔面积/m²·g^–1	介孔面积/m²·g^–1	平均孔径/nm
ZIF-8	1027.876	13.853	2.735
ZIF-8＋ZnO	1279.726	126.481	2.945
Co-Ni-N-C	297.970	96.965	2.748

样品	微孔面积/m²·g^–1	介孔面积/m²·g^–1	平均孔径/nm
ZIF-8	1027.876	13.853	2.735
ZIF-8＋ZnO	1279.726	126.481	2.945
Co-Ni-N-C	297.970	96.965	2.748

材料和投加量	氧化剂和用量	LEV浓度 /mg·L^-1	降解效率	参考文献
Co₃O₄/MnCo₂O₄（40g/L）	PMS（0.3g/L）	10	30mi，96.9%	[20]
MS-N₃H（0.8g/L）	PMS（0.4g/L）	20	90min，82.6%	[21]
CuO/MnFe₂O₄（1g/L）	PMS（1g/L）	5	120min，91.3%	[22]
Co-Ni-N-C（0.3g/L）	PMS（0.3g/L）	20	30min，97.1%	本工作