纳米管状Co-N-C活化过碳酸盐降解四环素

doi:10.16085/j.issn.1000-6613.2024-1146

摘要/Abstract

摘要：

过碳酸钠（SPC，Na₂CO₃·1.5H₂O₂）作为固体过氧化氢，近年来受到越来越多的关注。在此，通过简单的方法制备了具有丰富活性位点的纳米管状钴氮碳催化剂（Co-N-C），并用于活化SPC以有效去除四环素（TC）。通过透射电子显微镜（TEM）、扫描电子显微镜（SEM）对材料形貌进行表征。通过X射线粉末衍射仪（XRD）、傅里叶变换红外光谱仪（FTIR）和X射线光电子能谱（XPS）分析元素分布和价态变化。表征结果表明合成了具有丰富活性位点的纳米管状Co-N-C。在TC浓度10mg/L，SPC浓度为2mmol/L，Co-N-C含量为0.2g/L，pH为7的条件下，在20min内几乎实现了TC的100%降解。自由基淬灭实验和EPR测试表明Co-N-C/SPC系统中的 ·OH、·CO₃^-和·O₂^-为TC降解的主要活性物质。反应前后钴元素价态变化以及Co²⁺/Co³⁺循环过程促进了SPC的活化，三维荧光光谱分析表明TC在Co-N-C/SPC体系中被降解。

关键词: 过碳酸钠, 钴氮碳催化剂, 四环素, 动力学, 自由基作用

Abstract:

Sodium percarbonate (SPC, Na₂CO₃·1.5H₂O₂), known as solid hydrogen peroxide, has garnered increasing attention in recent years. In this study, a nanotubular cobalt-nitrogen-carbon catalyst (Co-N-C) with abundant active sites was prepared using a simple method and utilized to activate SPC for the effective removal of tetracycline (TC). The morphology of the material was characterized using transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The elemental distribution and valence state changes were analyzed using X-ray powder diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The characterization results indicated that a nanotubular Co-N-C with abundant active sites was successfully synthesized. Under the conditions of a TC concentration of 10mg/L, SPC concentration of 2mmol/L, Co-N-C content of 0.2g/L and pH of 7, nearly 100% degradation of TC was achieved within 20 minutes. Radical quenching experiments and electron paramagnetic resonance (EPR) tests revealed that ·OH, ·CO₃^- and ·O₂^- were the primary active species for TC degradation in the Co-N-C/SPC system. Changes in the valence state of cobalt before and after the reaction, as well as the Co²⁺/Co³⁺ cycling process, facilitated the activation of SPC, and three-dimensional fluorescence spectroscopy analysis indicated that TC was degraded in the Co-N-C/SPC system.

Key words: sodium percarbonate, cobalt-nitrogen-carbon catalyst, tetracycline, kinetics, radical action

中图分类号:

石秀顶, 王永全, 曾静, 苏畅, 洪俊明. 纳米管状Co-N-C活化过碳酸盐降解四环素[J]. 化工进展, 2025, 44(6): 3041-3052.

SHI Xiuding, WANG Yongquan, ZENG Jing, SU Chang, HONG Junming. Nanotubular Co-N-C activated percarbonate for tetracycline degradation[J]. Chemical Industry and Engineering Progress, 2025, 44(6): 3041-3052.

图/表 21

图1 样品的SEM、TEM和EDX mapping图像

图2 HAADF-STEM图像和EDX元素映射图像

图3 Co-N-C的N 1s光谱

图4 催化剂的N2吸附-脱附等温线

表1 不同样品的相对比表面积、平均孔容、平均孔径

样品	比表面积/m²·g^-1	孔容/cm³·g^-1	孔径/nm
CNT	50.14	0.13	5.50
Co-N-C	68.52	0.18	5.35

图5 Co-N-C的XRD图像和FTIR图像

图6 不同体系下TC的降解

表2 不同体系下污染物的降解效果

催化剂	污染物	氧化剂	实验条件	反应时间/min	去除率/%	参考文献
Fe₃O₄@α-MnO₂	RBK5	PMS	Cat.=1.2g/L；PMS=4mmol/L；pH=7；RBK5=30mg/L	60	91	[21]
Mn₂O₃@α-Fe₃O₄	RBK5	SPC	Cat.=0.3g/L；SPC=1mmol/L；pH=3；RBK5=10mg/L	90	88	[22]
FeS₂	TC	SPC	Cat.=0.5g/L；SPC=8mmol/L；pH=5；TC=10mg/L	60	78.86	[23]
Cu₃(MoO₄)₂(OH)₂	OTC	SPC	Cat.=0.25g/L；SPC=0.2g/L；pH=3；TC=20mg/L	40	80.01	[24]
CuCoFe-LDHs	CIP	SPC	Cat.=0.5g/L；SPC=0.3mmol/L；pH=5；CIP=20mg/L	60	66	[25]
Co-N-C	TC	SPC	Cat.=0.2g/L；SPC=0.2mmol/L；pH=7；TC=10mg/L	20	99.7	本文

图7 催化剂含量对Co-N-C/SPC体系性能和降解动力学的影响

图8 SPC浓度对Co-N-C/SPC体系性能和降解动力学的影响

图9 TC浓度对Co-N-C/SPC体系性能和降解动力学的影响

图10 pH对Co-N-C/SPC体系性能和降解动力学的影响

表3 不同pH下Co-N-C/SPC体系的降解动力学参数

pH	k/min^-1	R²
3	0.236	0.976
5	0.214	0.972
7	0.155	0.928
9	0.132	0.926
11	0.018	0.865

图11 不同水体和阴离子对Co-N-C/SPC系统性能的影响

图12 循环实验和催化剂反应前后表征谱图变化

表4 钴离子的浸出量

时间/min	Co²⁺浸出/mg·L^-1
3	0.046
5	0.078
10	0.083
15	0.097
20	0.103

图13 不同体系下TC的降解

图14 猝灭剂对TC去除的影响

图15 DMPO-·O2-，DMPO-·OH，DMPO-·CO3-和TEMP-1O2的EPR光谱

图16 反应前后Co-N-C的XPS分析

图17 降解前后TC的3D-EEM光谱

参考文献 36

[1]	LIN Zhong, CHEN Yijie, LI Gaoyang, et al. Change of tetracycline speciation and its impacts on tetracycline removal efficiency in vermicomposting with epigeic and endogeic earthworms[J]. Science of the Total Environment, 2023, 881: 163410.
[2]	YU Kan, LI Xiaoyong, QIU Yushu, et al. Low-dose effects on thyroid disruption in zebrafish by long-term exposure to oxytetracycline[J]. Aquatic Toxicology, 2020, 227: 105608.
[3]	HAN Chee-Hun, PARK Hee-Deung, KIM Song-Bae, et al. Oxidation of tetracycline and oxytetracycline for the photo-Fenton process: Their transformation products and toxicity assessment[J]. Water Research, 2020, 172: 115514.
[4]	HAN Q F, ZHAO S, ZHANG X R, et al. Distribution, combined pollution and risk assessment of antibiotics in typical marine aquaculture farms surrounding the Yellow Sea, North China[J]. Environment International, 2020, 138: 105551.
[5]	LIU Xiaohui, LIU Ying, LU Shaoyong, et al. Occurrence of typical antibiotics and source analysis based on PCA-MLR model in the East Dongting Lake, China[J]. Ecotoxicology and Environmental Safety, 2018, 163: 145-152.
[6]	YU Xiaolong, JIN Xu, LI Meng, et al. Mechanism and security of UV driven sodium percarbonate for sulfamethoxazole degradation using DFT and metabolomic analysis[J]. Environmental Pollution, 2023, 323: 121352.
[7]	QI Juanjuan, LIU Juzhe, SUN Fengbin, et al. High active amorphous Co(OH)₂ nanocages as peroxymonosulfate activator for boosting acetaminophen degradation and DFT calculation[J]. Chinese Chemical Letters, 2021, 32(5): 1814-1818.
[8]	CHEN Haoyun, YUAN Xingzhong, JIANG Longbo, et al. Intramolecular modulation of iron-based metal organic framework with energy level adjusting for efficient photocatalytic activity[J]. Applied Catalysis B: Environmental, 2022, 302: 120823.
[9]	Kwasi KYERE-YEBOAH, QIAO Xiuchen. Non-thermal plasma activated peroxide and percarbonate for tetracycline and oxytetracycline degradation: Synergistic performance, degradation pathways, and toxicity evaluation[J]. Chemosphere, 2023, 336: 139246.
[10]	XU Ximeng, ZHOU Yuhui, LI Shasha, et al. Activation of sodium percarbonate with Fe₃O₄@MXene composite for the efficient removal of bisphenol A[J]. Journal of Environmental Chemical Engineering, 2022, 10(6): 108702.
[11]	MOHAMMADI Samira, MOUSSAVI Gholamreza, YAGHMAEIAN Kamyar, et al. Development of a percarbonate-enhanced vacuum UV process for simultaneous fluoroquinolone antibiotics removal and fecal bacteria inactivation under a continuous flow mode of operation[J]. Chemical Engineering Journal, 2022, 431: 134064.
[12]	LI Yangju, DONG Haoran, LI Long, et al. Efficient degradation of sulfamethazine via activation of percarbonate by chalcopyrite[J]. Water Research, 2021, 202: 117451.
[13]	LIAO Gaozu, QING Xiaojiao, XU Peng, et al. Synthesis of single atom cobalt dispersed on 2D carbon nanoplate and degradation of acetaminophen by peroxymonosulfate activation[J]. Chemical Engineering Journal, 2022, 427: 132027.
[14]	张廷, 曾静, 叶校圳, 等. 纳米立方体PBA-Fe₁Mn₂活化过一硫酸盐降解偶氮有机物[J]. 中国环境科学, 2023, 43(7): 3533-3544.
	ZHANG Ting, ZENG Jing, YE Xiaozhen, et al. Nanoscale PBA-Fe₁Mn₂ activated peroxymonosulfate for degradation of azo organic[J]. China Environmental Science, 2023, 43(7): 3533-3544.
[15]	CHEN Shaona, LIANG Yanhua, LI Bo, et al. Facile synthesis of graphene oxide-supported CoO _x nanoparticles for efficient degradation of antibiotics via percarbonate activation: Performance, degradation pathway and mechanism[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2023, 675: 131996.
[16]	YANG Zhao, WANG Zhaowei, LIANG Guiwei, et al. Catalyst bridging-mediated electron transfer for nonradical degradation of bisphenol A via natural manganese ore-cornstalk biochar composite activated peroxymonosulfate[J]. Chemical Engineering Journal, 2021, 426: 131777.
[17]	XU Baokang, ZHANG Xiao, ZHANG Yue, et al. Enhanced electron transfer-based nonradical activation of peroxymonosulfate by CoN _x sites anchored on carbon nitride nanotubes for the removal of organic pollutants[J]. Chemical Engineering Journal, 2023, 466: 143155.
[18]	XU Haodan, JIANG Ning, WANG Da, et al. Improving PMS oxidation of organic pollutants by single cobalt atom catalyst through hybrid radical and non-radical pathways[J]. Applied Catalysis B: Environmental, 2020, 263: 118350.
[19]	GUO Xu, ZHANG Qicheng, HE Hongwei, et al. Wastewater flocculation substrate derived three-dimensional ordered macroporous Co single-atom catalyst for singlet oxygen-dominated peroxymonosulfate activation[J]. Applied Catalysis B: Environmental, 2023, 335: 122886.
[20]	XU Zhenyang, ZHANG Yimei, WANG Fei, et al. Co single-atom confined in N-doped hollow carbon sphere with superb stability for rapid degradation of organic pollutants[J]. Chemical Engineering Journal, 2023, 452: 139229.
[21]	董正玉, 吴丽颖, 王霁, 等. 新型Fe₃O₄@α-MnO₂活化过一硫酸盐降解水中偶氮染料[J]. 中国环境科学, 2018, 38(8): 3003-3010.
	DONG Zhengyu, WU Liying, WANG Ji, et al. Novel Fe₃O₄@α-MnO₂ activated peroxymonosulfate degradation of azo dyes in aqueous solution[J]. China Environmental Science, 2018, 38(8): 3003-3010.
[22]	徐铭骏, 郭兆春, 李立, 等. 纳米片状Mn₂O₃@α-Fe₃O₄活化过碳酸盐降解偶氮染料[J]. 化工进展, 2022, 41(2): 1043-1053.
	XU Mingjun, GUO Zhaochun, LI Li, et al. Degradation of azo dyes by sodium percarbonate activated with nanosheet Mn₂O₃@α-Fe₃O₄ [J]. Chemical Industry and Engineering Progress, 2022, 41(2): 1043-1053.
[23]	GUO Liu, NIE Ziqiu, WEN Lijia, et al. Insights into the effects of natural pyrite-activated sodium percarbonate on tetracycline removal from groundwater: Mechanism, pathways, and column studies[J]. Science of the Total Environment, 2023, 902: 165883.
[24]	JIN Xiaotao, WANG Yanlan, HUANG Yingping, et al. Percarbonate activation catalyzed by nanoblocks of basic copper molybdate for antibiotics degradation: High performance, degradation pathways and mechanism[J]. Chinese Chemical Letters, 2024, 35(10): 109499.
[25]	CHEN Kang, LI Ting, ZHANG Xue, et al. CuCoFe-LDHs activated sodium percarbonate (SPC) for the degradation of ciprofloxacin[J]. Journal of Environmental Chemical Engineering, 2023, 11(5): 110651.
[26]	WU Liying, ZHANG Qian, HONG Junming, et al. Degradation of bisphenol A by persulfate activation via oxygen vacancy-rich CoFe₂O_4- _x [J]. Chemosphere, 2019, 221: 412-422.
[27]	DUAN Xiaoguang, SU Chao, ZHOU Li, et al. Surface controlled generation of reactive radicals from persulfate by carbocatalysis on nanodiamonds[J]. Applied Catalysis B: Environmental, 2016, 194: 7-15.
[28]	LIN Kun-Yi Andrew, LIN Jyun-Ting, LIN Yifeng. Heterogeneous catalytic activation of percarbonate by ferrocene for degradation of toxic amaranth dye in water[J]. Journal of the Taiwan Institute of Chemical Engineers, 2017, 78: 144-149.
[29]	BAI Rui, YAN Weifu, XIAO Yong, et al. Acceleration of peroxymonosulfate decomposition by a magnetic MoS₂/CuFe₂O₄ heterogeneous catalyst for rapid degradation of fluoxetine[J]. Chemical Engineering Journal, 2020, 397: 125501.
[30]	SHAH Noor S, KHAN Javed Ali, SAYED Murtaza, et al. Hydroxyl and sulfate radical mediated degradation of ciprofloxacin using nano zerovalent manganese catalyzed S₂O₈ ^2- [J]. Chemical Engineering Journal, 2019, 356: 199-209.
[31]	WANG Jianlong, WANG Shizong. Effect of inorganic anions on the performance of advanced oxidation processes for degradation of organic contaminants[J]. Chemical Engineering Journal, 2021, 411: 128392.
[32]	廖兵, 胥雯, 叶秋月. 活化过碳酸盐及过氧碳酸氢盐在水处理领域中的研究进展[J]. 化工进展, 2022, 41(6): 3235-3248.
	LIAO Bing, XU Wen, YE Qiuyue. A review of activated percarbonate and peroxymonocarbonate in the field of water treatment[J]. Chemical Industry and Engineering Progress, 2022, 41(6): 3235-3248
[33]	MO Zhihua, TAN Zexing, LIANG Jialin, et al. Iron-rich sludge biochar triggers sodium percarbonate activation for robust sulfamethoxazole removal: Collaborative roles of reactive oxygen species and electron transfer[J]. Chemical Engineering Journal, 2023, 457: 141150.
[34]	LI Li, GUO Ruoning, ZHANG Sai, et al. Sustainable and effective degradation of aniline by sodium percarbonate activated with UV in aqueous solution: Kinetics, mechanism and identification of reactive species[J]. Environmental Research, 2022, 207: 112176.
[35]	ASIF Abdul Hannan, RAFIQUE Nasir, HIRANI Rajan Arjan Kalyan, et al. Heterogeneous activation of peroxymonosulfate by Co-doped Fe₂O₃ nanospheres for degradation of p-hydroxybenzoic acid[J]. Journal of Colloid and Interface Science, 2021, 604: 390-401.
[36]	SHE Yuecheng, WEI Wenxuan, AI Xiaohuan, et al. Synergistic pretreatment of CaO and freezing/thawing to enhance volatile fatty acids recycling and dewaterability of waste activated sludge via anaerobic fermentation[J]. Chemosphere, 2021, 280: 130939.