表面修饰FeOCl活化过硫酸盐引发有机污染物非自由基降解

doi:10.16085/j.issn.1000-6613.2024-1486

摘要/Abstract

摘要：

类芬顿反应中，铁基催化剂活性中心所在的化学环境对体系的反应机理具有深远的影响。基于该影响，本研究通过使用吸电子有机物硝基对苯二甲酸（NTPA）对二维层状铁基材料FeOCl表面进行修饰，制备出易分离回收的铁基催化剂（NTPA-FeOCl），利用SEM、XRD、XPS、FTIR表征分析其形貌和微观结构，通过活化过一硫酸盐（PMS）降解对乙酰氨基酚（ACT），来评价其催化性能。另外，通过控制实验变量和引入不同抗生素、内分泌干扰物、护理品类有机污染物，系统考察了NTPA-FeOCl活化PMS体系降解有机物的效能、特点。结果表明，在NTPA-FeOCl投加量0.2g/L，PMS浓度2mmol/L，以及初始pH=7.0的条件下，ACT（0.1mmol/L）可在30min内降解99.69%，且体系对不同有机物的降解表现出选择性。淬灭实验结果表明，体系内ACT的降解由自由基和非自由基共同完成，但单线氧是主导活性氧物种，因此进一步证明了体系对富电子型有机物的选择氧化性。NTPA修饰后，FeOCl表面部分Fe原子呈现缺电子状态，吸引PMS端头O原子发生反应，从而提高了体系内单线氧的生成量，强化了有机物降解的非自由基路径。

关键词: 类芬顿, 氧基氯化铁, 过一硫酸盐, 单线氧, 非自由基路径

Abstract:

In Fenton-like reactions, the chemical environment surrounding the active sites of iron-based catalysts profoundly influences the mechanism of the reaction system. In light of this impact, this study functionalized the surface of the two-dimensional layered iron-based material FeOCl with the electron-withdrawing organic compound nitroterephthalic acid (NTPA) to synthesize an easily separable and recoverable iron-based catalyst (NTPA-FeOCl). The morphology and microstructure of the catalyst were characterized using SEM, XRD, XPS and FTIR. The catalytic performance was assessed by activating persulfate (PMS) to degrade acetaminophen (ACT). Furthermore, by controlling experimental variables and introducing a variety of antibiotics, endocrine disruptors, and personal care product organic pollutants, the study systematically examined the efficacy and characteristics of the NTPA-FeOCl activated PMS system in degrading organic compounds. The results demonstrated that under the conditions of 0.2g/L NTPA-FeOCl, 2mmol/L PMS concentration, and an initial pH of 7.0, ACT (0.1mmol/L) was degraded by 99.69% within 30 minutes, exhibiting selectivity in the degradation of different organic substances. Quenching experiments revealed that the degradation of ACT within the system was mediated by both radicals and selective oxidative activity non-radicals of the system, with singlet oxygen being the predominant reactive oxygen species, thereby further the towards electron-rich organic compounds. After modification with NTPA, some Fe atoms on the FeOCl surface were in an electron-deficient state, which attracted the terminal O atoms of PMS for reaction, consequently enhancing the generation of singlet oxygen within the system and fortifying the non-radical pathway for organic degradation.

Key words: Fenton-like reaction, FeOCl, peroxymonosulfate, singlet oxygen, non-radical pathways

中图分类号:

X703.1

王御豪, 蒋沁利, 徐西蒙. 表面修饰FeOCl活化过硫酸盐引发有机污染物非自由基降解[J]. 化工进展, 2025, 44(6): 3101-3111.

WANG Yuhao, JIANG Qinli, XU Ximeng. Degradation of organic pollutants via non-radical pathway by surface modified FeOCl activating persulfate[J]. Chemical Industry and Engineering Progress, 2025, 44(6): 3101-3111.

图/表 14

表1 各污染物高效液相色谱仪流动相参数

污染物名称	体积分数/%				检测波长/nm	流速/mL·min^-1	进样时间/min
污染物名称	乙腈	甲醇	乙酸（1%）-水溶液	水	检测波长/nm	流速/mL·min^-1	进样时间/min
SMX	40	—	60	—	264	1	5.5
ACT	15	—	85	—	254	1	7
BPA	—	75	—	25	225	1	6
BPS	—	55	45	—	258	0.8	5.5
IBU	—	80	20	—	220	1	7
ATZ	—	70	—	30	225	1	6
CBZ	60	—	—	40	286	1	5.5
2.4-DCP	60	—	40	—	284	1	7
PMSO	28	—	—	72	215	1	8.5
PMSO₂	25	—	—	75	230	1	10

图1 催化剂的SEM图像

图2 不同制备时间的NTPA-FeOCl催化剂的XRD图及NTPA-FeOCl(4h)催化剂的FTIR图

图3 不同反应体系内ACT的降解效能{[ACT]=0.1mmol/L，[PMS]=2mmol/L，[NTPA-FeOCl]=[FeOCl]=0.2g/L， pH=7.0，T=25℃}

图4 反应参数对NTPA-FeOCl/PMS体系降解ACT效能的影响

表2 不同反应参数下NTPA-FeOCl/PMS体系降解ACT的拟一级动力学拟合参数

单因素条件	变量	k_obs/min^-1	R²
PMS投加浓度	0.5mmol/L	0.0485	0.9932
	1mmol/L	0.0672	0.9929
	2mmol/L	0.1457	0.9939
	4mmol/L	0.2599	0.9763
	8mmol/L	0.1852	0.9818
初始pH	3.0	0.1684	0.9938
	5.0	0.1542	0.9943
	7.0	0.1457	0.9939
	8.0	0.0488	0.9998
	10.0	1.2322	0.9999
NTPA-FeOCl投加量	0.1g/L	0.0451	0.9992
	0.2g/L	0.1457	0.9939
	0.3g/L	0.1917	0.9776
	0.4g/L	0.2882	0.9944
	0.5g/L	0.4674	0.9698

图5 NTPA-FeOCl/PMS体系对不同污染的降解效果{[BPS]=[IBU]=[2,4-DCP]=[ACT]=[CBZ]=[BPA]=[SMX]=[ATZ]=0.1mmol/L，[PMS]=2mmol/L，[NTPA-FeOCl]=0.2g/L，pH=7.0，T=25℃}

图6 NTPA-FeOCl体系内醇类、醌类淬灭剂对ACT降解效能的影响{[ACT]=0.1mmol/L，[PMS]=2mmol/L，[NTPA-FeOCl]=0.2g/L，pH=7.0，T=25℃}

图7 β-胡萝卜素淬灭剂对ACT降解效能的影响{[ACT]=0.1mmol/L，[PMS]=2mmol/L，[FeOCl]=[NTPA-FeOCl]=0.2g/L，pH=7.0，T=25℃}

图8 NTPA-FeOCl/PMS体系中PMSO的消耗与PMSO2的生成{[PMSO]0=1mmol/L，[PMSO2]0=0mmol/L，[PMS]=2mmol/L，[NTPA-FeOCl]=0.2g/L，pH=7.0，T=25℃}

图9 FeOCl及NTPA-FeOCl的XPS图（Fe 2p）

图10 体系内ROS的生成路径

图11 不同溶液（H2O和D2O）中ACT的降解效能及不同体系内TEMP-1O2的EPR谱图{[ACT]=0.1mmol/L，[PMS]=2mmol/L，[FeOCl]=[NTPA-FeOCl]=0.1g/L，pH=7.0，T=25℃}

图12 NTPA催化剂循环回用实验及Fe2+浸出浓度变化{[ACT]=0.1mmol/L，[PMS]=2mmol/L，[NTPA-FeOCl]=0.2g/L，pH=7.0，T=25℃}

参考文献 33

[1]	WANG Jianlong, WANG Shizong. Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging contaminants[J]. Chemical Engineering Journal, 2018, 334: 1502-1517.
[2]	DUAN Xiaoguang, SUN Hongqi, SHAO Zongping, et al. Nonradical reactions in environmental remediation processes: Uncertainty and challenges[J]. Applied Catalysis B: Environmental, 2018, 224: 973-982.
[3]	LIANG Jun, DUAN Xiaoguang, XU Xiaoyun, et al. Persulfate oxidation of sulfamethoxazole by magnetic iron-char composites via nonradical pathways: Fe(Ⅳ) versus surface-mediated electron transfer[J]. Environmental Science & Technology, 2021, 55(14): 10077-10086.
[4]	LIU Lindong, LIU Qian, WANG Ying, et al. Nonradical activation of peroxydisulfate promoted by oxygen vacancy-laden NiO for catalytic phenol oxidative polymerization[J]. Applied Catalysis B: Environmental, 2019, 254: 166-173.
[5]	YAN Yiqi, WEI Zongsu, DUAN Xiaoguang, et al. Merits and limitations of radical vs. nonradical pathways in persulfate-based advanced oxidation processes[J]. Environmental Science & Technology, 2023, 57(33): 12153-12179.
[6]	DOU Jibo, CHENG Jie, LU Zhijiang, et al. Biochar co-doped with nitrogen and boron switching the free radical based peroxydisulfate activation into the electron-transfer dominated nonradical process[J]. Applied Catalysis B: Environmental, 2022, 301: 120832.
[7]	WANG Jinling, HOU Kaipeng, WEN Yuzhen, et al. Interlayer structure manipulation of iron oxychloride by potassium cation intercalation to steer H₂O₂ activation pathway[J]. Journal of the American Chemical Society, 2022, 144(10): 4294-4299.
[8]	MA Yahui, WANG Dalin, XU Yin, et al. Nonradical electron transfer-based peroxydisulfate activation by a Mn-Fe bimetallic oxide derived from spent alkaline battery for the oxidation of bisphenol A[J]. Journal of Hazardous Materials, 2022, 436: 129172.
[9]	WU Que, ZHANG Yongqing, MENG Hong, et al. Cu/N co-doped biochar activating PMS for selective degrading paracetamol via a non-radical pathway dominated by singlet oxygen and electron transfer[J]. Chemosphere, 2024, 357: 141858.
[10]	YIN Yue, Ruolin LYU, ZHANG Weiming, et al. Exploring mechanisms of different active species formation in heterogeneous Fenton systems by regulating iron chemical environment[J]. Applied Catalysis B: Environmental, 2021, 295: 120282.
[11]	王金岭, 温玉真, 汪华林, 等. FeOCl层状材料及其插层化合物: 结构、性质与应用[J]. 化学进展, 2021, 33(2): 263-280.
	WANG Jinling, WEN Yuzhen, WANG Hualin, et al. FeOCl and its intercalation compounds: Structures, properties and applications[J]. Progress in Chemistry, 2021, 33(2): 263-280.
[12]	YANG Xuejing, XU Ximeng, XU Jing, et al. Iron oxychloride (FeOCl): An efficient Fenton-like catalyst for producing hydroxyl radicals in degradation of organic contaminants[J]. Journal of the American Chemical Society, 2013, 135(43): 16058-16061.
[13]	XU Ximeng, ZHANG Shujing, WANG Yuhao, et al. 2D Surfaces twisted to enhance electron freedom toward efficient advanced oxidation processes[J]. Applied Catalysis B: Environment and Energy, 2024, 345: 123701.
[14]	杨本谱. 铁(Ⅲ)-邻菲罗啉光化还原分光光度法测定铁[J]. 冶金分析, 1990, 10(4): 53-54.
	YANG Benpu. Photoreduction spectrophotometric determination of iron (Ⅲ) with phenanthroline[J]. Metallurgical Analysis, 1990, 10(4): 53-54.
[15]	BECHAMBI Olfa, JLAIEL Lobna, NAJJAR Wahiba, et al. Photocatalytic degradation of bisphenol A in the presence of Ce-ZnO: Evolution of kinetics, toxicity and photodegradation mechanism[J]. Materials Chemistry and Physics, 2016, 173: 95-105.
[16]	LI Yan, ZHANG Han, RASHID Azhar, et al. Bisphenol A attenuation in natural microcosm: Contribution of ecological components and identification of transformation pathways through stable isotope tracing[J]. Journal of Hazardous Materials, 2020, 385: 121584.
[17]	GAO Kaihua, CHEN Jitao, LIU Zhongmin, et al. Intensified redox co-conversion of As(Ⅲ) and Cr(Ⅵ) with MIL-125(Ti)-derived COOH functionalized TiO₂: Performance and mechanism[J]. Chemical Engineering Journal, 2019, 360: 1223-1232.
[18]	ZHANG Xiaodong, YUE Ke, RAO Renzhi, et al. Synthesis of acidic MIL-125 from plastic waste: Significant contribution of N orbital for efficient photocatalytic degradation of chlorobenzene and toluene[J]. Applied Catalysis B: Environmental, 2022, 310: 121300.
[19]	周宇辉, 林洋仟, 王御豪, 等. 磁性复合材料活化过硫酸盐去除水中双酚A[J]. 中国环境科学, 2024, 44(2): 832-840.
	ZHOU Yuhui, LIN Yangqian, WANG Yuhao, et al. Removing bisphenol A with magnetic sandwich composite activated peroxymonosulfate[J]. China Environmental Science, 2024, 44(2): 832-840.
[20]	XU Ximeng, ZONG Shaoyan, CHEN Weiming, et al. Comparative study of bisphenol A degradation via heterogeneously catalyzed H₂O₂ and persulfate: Reactivity, products, stability and mechanism[J]. Chemical Engineering Journal, 2019, 369: 470-479.
[21]	XU Ximeng, CHEN Weiming, ZONG Shaoyan, et al. Magnetic clay as catalyst applied to organics degradation in a combined adsorption and Fenton-like process[J]. Chemical Engineering Journal, 2019, 373: 140-149.
[22]	QI Chengdu, LIU Xitao, MA Jun, et al. Activation of peroxymonosulfate by base: Implications for the degradation of organic pollutants[J]. Chemosphere, 2016, 151: 280-288.
[23]	LEI Yu, YU Yafei, LEI Xin, et al. Assessing the use of probes and quenchers for understanding the reactive species in advanced oxidation processes[J]. Environmental Science & Technology, 2023, 57(13): 5433-5444.
[24]	GARAVELLI Marco, BERNARDI Fernando, OLIVUCCI Massimo, et al. DFT study of the reactions between singlet-oxygen and a carotenoid model[J]. Journal of the American Chemical Society, 1998, 120(39): 10210-10222.
[25]	HUANG Bingkun, REN Xinyi, ZHAO Jian, et al. Modulating electronic structure engineering of atomically dispersed cobalt catalyst in Fenton-like reaction for efficient degradation of organic pollutants[J]. Environmental Science & Technology, 2023, 57(37): 14071-14081.
[26]	FANG Qianzhen, YANG Hailan, YE Shujing, et al. Generation and identification of ¹O₂ in catalysts/peroxymonosulfate systems for water purification[J]. Water Research, 2023, 245: 120614.
[27]	BI Guangyu, DING Rongrong, SONG Junsheng, et al. Discriminating the active Ru species towards the selective generation of singlet oxygen from peroxymonosulfate: Nanoparticles surpass single-atom catalysts[J]. Angewandte Chemie, 2024, 136(17): 2401551.
[28]	WANG Zhen, QIU Wei, PANG Suyan, et al. Further understanding the involvement of Fe(Ⅳ) in peroxydisulfate and peroxymonosulfate activation by Fe(Ⅱ) for oxidative water treatment[J]. Chemical Engineering Journal, 2019, 371: 842-847.
[29]	YAO Jiayi, WU Nannan, TANG Xiaosheng, et al. Methyl phenyl sulfoxide (PMSO) as a quenching agent for high-valent metal-oxo species in peroxymonosulfate based processes should be reconsidered[J]. Chemical Engineering Journal Advances, 2022, 12: 100378.
[30]	Wen-Da OH, DONG Zhili, Teik-Thye LIM. Generation of sulfate radical through heterogeneous catalysis for organic contaminants removal: Current development, challenges and prospects[J]. Applied Catalysis B: Environmental, 2016, 194: 169-201.
[31]	HU Jian, ZENG Xiangkang, WANG Gen, et al. Modulating mesoporous Co₃O₄ hollow nanospheres with oxygen vacancies for highly efficient peroxymonosulfate activation[J]. Chemical Engineering Journal, 2020, 400: 125869.
[32]	YAO Yiyuan, WANG Chaohai, YAN Xin, et al. Rational regulation of Co-N-C coordination for high-efficiency generation of ¹O₂ toward nearly 100% selective degradation of organic pollutants[J]. Environmental Science & Technology, 2022, 56(12): 8833-8843.
[33]	WU Zelin, XIONG Zhaokun, LIU Wen, et al. Active center size-dependent Fenton-like chemistry for sustainable water decontamination[J]. Environmental Science & Technology, 2023, 57(50): 21416-21427.