高级氧化体系中活性氧化物质的定性和半定量分析方法研究进展

周晨颖; 周鹏; 张鹏; 孙一鸣; 赖波

doi:10.13198/j.issn.1001-6929.2023.02.14

高级氧化体系中活性氧化物质的定性和半定量分析方法研究进展

doi: 10.13198/j.issn.1001-6929.2023.02.14

周晨颖^{1, 2,},
周鹏^{1, 2},
张鹏^{1, 2},
孙一鸣^{1, 2},
赖波^{1, 2, ,}

1.
四川大学建筑与环境学院，四川成都　610065
2.
四川大学中德水环境与健康研究中心，四川成都　610041

基金项目: 国家自然科学基金项目(No.51878423, 52070133)

详细信息

作者简介:
周晨颖（1997-），女，四川成都人，zhouchenying1997@163.com

通讯作者:
赖波(1982-)，男，四川成都人，教授，博士，博导，主要从事水处理理论与技术研究，laibo@scu.edu.cn

中图分类号: X830.2
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- 文章访问数: 192
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- 被引次数: 0
出版历程
- 收稿日期: 2022-12-14
- 修回日期: 2023-02-27

Advances in Qualitative and Semi-Quantitative Analysis of Reactive Oxygen Species in Advanced Oxidation Processes

ZHOU Chenying^{1, 2
,},
ZHOU Peng^{1, 2},
ZHANG Peng^{1, 2},
SUN Yiming^{1, 2},
LAI Bo^{1, 2
, ,}

1.
College of Architecture and Environment, Sichuan University, Chengdu 610065, China
2.
Sino-German Centre for Water and Health Research, Sichuan University, Chengdu 610041, China

Funds: National Natural Science Foundation of China (No.51878423, 52070133)

摘要

摘要: 对高级氧化反应体系中活性氧化物质(ROS)的类型、贡献占比和反应途径的定性与半定量分析对于探究有机污染物的降解过程与具体机制至关重要. 基于文献调研，本文总结了高级氧化体系中多种ROS的氧化还原电位、反应机制等主要特点，综述了ROS的定性和半定量分析方法，包括电子顺磁性共振技术、ROS选择性淬灭方法、化学探针法、电化学法、原位拉曼法、穆斯堡尔光谱法、同步辐射法和定量构效关系分析法，分析了其优缺点和应用场景. 结果表明：①高级氧化体系中通常存在ROS的协同作用，这会在一定程度上干扰ROS的定量分析结果. ②由于分析难度高、影响因素繁多，目前缺乏快速准确的ROS定量检测技术. 为更加科学合理地开展有机污染降解机理探究和应用技术开发工作，今后应以ROS快速定量检测技术和原位技术为研究重点，结合模型方法等辅助手段分析高级氧化体系中的活性氧化物质暴露量或瞬态浓度及其对污染物去除的贡献，以及预测污染物去除效率等.
- 高级氧化技术 /
- 活性氧化物质 /
- 机理探究 /
- 分析方法
Abstract: Qualitative and semi-quantitative analysis of the type, contributions and reaction pathways of reactive oxygen species (ROS) is crucial to explore contaminant degradation mechanisms. Based on the previous literature, this study summarized the main characteristics of ROS (redox potentials and reaction mechanisms), and reviewed the qualitative and semi-quantitative analysis methods of ROS, including electron paramagnetic resonance, quenching, chemical probe, electrochemical, in situ Raman, Mossbauer spectroscopy, synchrotron radiation and quantitative structure-activity relationship analysis methods. Their advantages, shortcomings and application scenarios were discussed. The results show that: (1) The synergistic effect of ROS usually exists in advanced oxidation systems, which will interfere with the quantitative analysis results of ROS to a certain extent. (2) Due to the high analysis difficulty and numerous influencing factors, there is a lack of rapid and accurate quantitative detection technique for ROS. In order to explore the mechanism of organic pollution degradation and develop application technologies in a more scientific and reasonable way, rapid quantitative detection technology and in situ technique for ROS should be the research focus in the future, combined with model methods to analyze the exposure amount or transient concentration of ROS in advanced oxidation systems and their contribution to pollutant removal, and to predict the efficiency of pollutant removal.
- advanced oxidation technology /
- reactive oxygen species /
- mechanism exploration /
- analytical method

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图 1 高级氧化体系中典型ROS与有机物和无机离子反应的速率常数^[18-24]

Figure 1. Rate constants of typical ROS for reacting with organic matter or inorganic ions in advanced oxidation systems^[18-24]

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表 1 高级氧化体系中常见的活性氧化物质(ROS)

Table 1. Common reactive oxygen species in advanced oxidation systems (ROS)

AOPs	主要ROS	数据来源
芬顿氧化	^•OH、Fe(Ⅳ)和O₂^•−	文献[4]
过硫酸盐氧化	SO₄^•−、过氧单硫酸根自由基(SO₅^•−)、^•OH和¹O₂	文献[5]
过氧乙酸氧化	^•OH、乙酰氧基、乙酰过氧基	文献[6]
臭氧氧化	臭氧(O₃)、^•OH、O₂^•−和臭氧自由基(O₃^•−)	文献[7-8]
光催化氧化	^•OH、光生电子(e_CB)、电子空穴(h_VB⁺)和SO₄^•−	文献[9-10]
电化学氧化	^•OH、电子(e)和双氧水(H₂O₂)	文献[11]
辐射辅助氧化	^•OH、水合电子(e_aq)、氢自由基(H^•)和H₂O₂	文献[12]
超声波辅助氧化	^•OH、O₂^•−、H^•和H₂O₂	文献[13]
其他	表面活性中间体、持久自由基(PFRs)、高价金属和Cl^•等	文献[14-17]

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表 2 高级氧化体系中典型ROS的基本理化性质

Table 2. Basic physicochemical properties of common ROS in advanced oxidation systems

ROS	氧化还原电位(E⁰)	寿命	机制	主要特点	数据来源
^•OH	E⁰(^•OH/H₂O)=2.73 V	20 ns	夺氢、加成、电子转移	扩散限制(<25 nm)	文献[4,16,21,25-28]
SO₄^•−	E⁰(SO₄^•−/SO₄²⁻)=2.50 V	30～40 μs	电子转移、夺氢、加成	易受到水中腐殖质等共存有机污染物质的干扰	文献[25,27-29]
O₂^•−	E⁰(O₂^•−/H₂O₂) = 0.91 V	1 s	夺氢	反应性较弱；生成氧化还原反应的常见中间产物	文献[30-31]
CO₃^•−	E⁰(CO₃^•−/HCO₃⁻)=1.78 V	1～10 μs	电子转移	CO₃^•−与苯胺和含硫化合物的反应速率较快	文献[28,32]
含卤素自由基 (Cl^•、Cl₂^•−、Br^•)	E⁰(Cl^•/Cl⁻)=2.5 V、 E⁰(Cl₂^•−/Cl⁻)=2.2 V、 E⁰(Br^•/Br⁻)=2.0 V	—	夺氢、加成电子转移	反应速率常数的范围〔<10³~10¹⁰ L/(mol·s)〕较广；Cl^•反应最迅速〔10⁸~10¹⁰ L/(mol·s)〕，X^•比X₂^•−反应更快；极易产生有高致癌性、细胞毒性和致突变性的卤化产物，但也有研究表明引入Cl⁻可以提升高级氧化效果且不产生消毒副产物	文献[16,33]
含氮自由基 (NO₃^•、NO₂^•、NO^•)	E⁰(NO₃^•/NO₃⁻)=2.3~2.5 V、 E⁰(NO₂^•/NO₂⁻)=1.03 V、 E⁰(NO^•/NO⁻)=0.39 V	—	电子转移	极易产生有高致癌性、细胞毒性和致突变性的(亚)硝化产物	文献[34]

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续表
ROS	氧化还原电位(E⁰)	寿命	机制	主要特点	数据来源
PFRs	—	几天至几月	电子转移、电子介导	有机物质部分碳化形成以碳/氧为中心自由基或碳中心非共电子对，如半醌、环戊二烯基和苯氧基；反应活性较高	文献[35]
H^•	E⁰(H^•/e_aq⁻)=−2.10 V	—	加氢还原	快速降解含吸电子基团的有机化合物	文献[21]
SO₅^•−	E⁰(SO₅^•−/SO₄²⁻)=1.22 V	—	氧化	氧化能力低	文献[36]
H₂O₂	E⁰(H₂O₂/H⁺)=1.78 V	小时级	氧化	氧化能力低	文献[36]
¹O₂	E⁰(¹O₂/O₂^•−)=0.81 V	2~3.5 μs	氧化	在芳香族化合物的链引发和增长过程中起重要作用	文献[31,37]
以Fe(Ⅳ)为代表的高价金属	E⁰〔Fe(Ⅳ)/Fe(Ⅲ)〕=1.80 V	7 s	电子转移、亲电加成	氧化能力较弱	文献[4,25,36,38]
O₃	E⁰(O₃/O₃^•−)=1.03 V	<1 h	氧化	稳定性取决于水基质pH和天然有机物	文献[7,26]
表面活性中间体	碳纳米管(CNT)-过二硫酸盐(PDS)复合物，E⁰=0.65 V	—	氧化	温和且具有选择性；扩散限制(<1 μm)	文献[5,14]

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表 3 多种捕获剂与ROS的特征反应

Table 3. Characteristic reaction between various trapping agents and ROS

ROS	g值	特征反应路径	自旋加合物及其特征强度比	自旋加合物EPR谱图示例	数据来源
^•OH	2.0061		5,5-二甲基-1-吡咯啉-N-氧化物(DMPO)-OH，其特征强度比为1:2:2:1		文献[39-40]
SO₄^•−	2.0084		DMPO-SO₄，其特征强度比为1:1:1:1:1:1		文献[40]
O₂^•−	2.0053		DMPO-O₂，其特征强度比为1:1:1:1		文献[41]
¹O₂	2.0056		2,2,6,6-四甲基哌啶氧化物(TEMP)-¹O₂，其特征强度比为1:1:1		文献[42]
PFR	2.0033	直接测定，浓度范围为10¹⁶~10¹⁹ spins/g	—		文献[15]

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表 4 ROS与典型淬灭剂反应的速率常数(k)

Table 4. Rate constants of reaction between ROS and quenchers

目标ROS	淬灭剂	k/[L/(mol·s)]				数据来源
目标ROS	淬灭剂	^•OH	SO₄^•−	O₂^•−	¹O₂	数据来源
^•OH和SO₄^•−	叔丁醇	6×10⁸	4×10⁵	—	3.04×10³	文献[10,48]
	异丙醇	1.9×10⁹	8.2×10⁷	—	3.48×10³	文献[48]
	甲醇	9.7×10⁸	1.1×10⁷	—	3.89×10³	文献[10,48]
	乙醇	2.8×10⁹	7.7×10⁷	—	3.80×10³	文献[48]
O₂^•−	对苯醌	1.2×10⁹	—	8.3×10⁸	3.4×10⁷	文献[49]
O₂^•−	氯仿	< 2×10⁶	—	1.1×10⁹	—	文献[10]
¹O₂	叠氮化钠	1.2×10¹⁰	2.5×10⁹	—	2×10⁸	文献[50]
	L-组氨酸	7.1×10⁹	2.5×10⁹	—	3.2×10⁷	文献[48]
	糠醇	1.5×10¹⁰	1.3×10¹⁰	3.5×10³	1.2×10⁸	文献[48]

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表 5 ROS的化学探针反应

Table 5. Chemical probe reaction of ROS

首步反应类型	ROS	探针及主要产物	数据来源
加成	^•OH	苯甲酸(羟基化产物)	文献[4]
	^•OH	水杨酸(2,3-二羟基苯甲酸和2,5-二羟基苯甲酸)	文献[52-53]
	^•OH	对苯二甲酸(2-羟基对苯二甲酸)	文献[54]
取代	^•OH	二甲基亚砜(甲醛，其再与2,4-二硝基苯肼反应生成特征产物腙)	文献[52]
消除	H₂O₂	硼基苯并[b]喹啉鎓衍生物(苯并[b]喹啉鎓衍生物)	文献[55]
聚合	H₂O₂	4-羟基-3-甲氧基-苯乙酸(辣根过氧化物酶存在时生成荧光二聚体)	文献[56]
氧化	高价金属	二甲基亚砜(二甲基砜)	文献[4,17]
氧化	¹O₂	9,10-二甲基蒽(9,10-二甲基蒽的内过氧化物)	文献[57]
还原	O₂^•−	氯化硝基四唑蓝(蓝色单臜)	文献[53]
还原	O₂^•−	四硝基甲烷(硝基甲烷阴离子)	文献[58]

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表 6 ROS与有机物反应的构效关系

Table 6. Structure-activity relationship between ROS and organic compounds

ROS	目标物	描述符及相关性	相关解释	数据来源
活性中间体	溴酚	lg(k_obs/k)与E_1/2呈负相关	单电子氧化为主	文献[68]
SO₄^•−	芳香族化合物	吉普斯自由能(ΔG)与E_HOMO呈负相关	亲电取代为主	文献[67]
含氯自由基和H₂PO₄^•	芳香胺类化合物	lg(k_obs/k)与E_HOMO不相关	自由基亲电攻击可能性小	文献[69]
O₃和CO₃^•−	芳香胺类化合物	lg(k_obs/k)与E_HOMO呈正相关	自由基亲电攻击可能性大	文献[69]
SO₄^•−	芳烃和酰胺类化合物	k_obs与E_HOMO和IP均不相关，与E_LOMO和E_HOMO的差值呈负相关	无主导反应	文献[29]
Cl^•	酚类、烷氧基苯类和苯胺类化合物	k_obs与σ⁺不相关	给/吸电子官能团不影响反应	文献[33]
Cl₂^•−	酚类、烷氧基苯类和苯胺类化合物	k_obs与σ⁺呈负相关	亲电反应为主	文献[33]
O₃和HFeO₄⁻	酚类化合物	k_obs与σ⁺呈负相关	亲电反应为主	文献[70]
O₃	烯烃	k_obs与σ^*呈负相关	与具有给电子取代基的烯烃反应较快	文献[70]
活性中间体	酚和苯胺类化合物	lg k_obs与σ⁺和σ⁻均呈负相关	与具有给电子取代基的芳香族化合物反应更快	文献[68]

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