活化分子氧降解水中典型新污染物研究进展

李惠; 杨林峰; 刘佳佳; 及吉祥; 沈铸睿

doi:10.13198/j.issn.1001-6929.2021.08.29

活化分子氧降解水中典型新污染物研究进展

doi: 10.13198/j.issn.1001-6929.2021.08.29

南开大学材料科学与工程学院, 天津 300350

基金项目:

国家自然科学基金项目 21872102

详细信息

作者简介:
李惠(1990-), 女, 河北新乐人, 1551664924@qq.com

通讯作者:
沈铸睿(1982-), 男, 辽宁朝阳人, 研究员, 博士, 博导, 主要从事环境催化与污染控制研究, 019019@nankai.edu.cn

中图分类号: X52
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- 被引次数: 0
出版历程
- 收稿日期: 2021-07-01
- 修回日期: 2021-08-27

Research Progress of Molecular Oxygen Activation for Degradation of Typical Emerging Contaminants in Water

School of Materials Science and Engineering, Nankai University, Tianjin 300350, China

Funds:

National Natural Science Foundation of China 21872102

摘要

摘要: 近年来，新污染物在水体中被频繁检出，其化学性质稳定、易生物积累，给生态环境和人类健康带来严重威胁. 为解决此问题，高级氧化技术逐渐发展为一种有前景的环境修复方法，在众多氧化剂中，分子氧(O₂)是丰富、经济、绿色的氧化剂. O₂主要经由催化促进的电子转移和能量转移途径而被活化，进而转化为活性氧物种(ROS). 活化O₂转化为ROS，有望成为清除水中新污染物富有潜力的研究方法和实用技术. 目前，研发更高效催化材料(或其他类型活化材料)，以实现对O₂的高效活化和对污染物的彻底、快速降解是相关领域研究的关注焦点. 本文重点介绍了活化O₂降解水中新污染物的基本概念和最新研究进展，包括O₂可转化生成的主要ROS、O₂活化策略、活化O₂用于降解新污染物的研究成果等，并对O₂活化所遇到的核心问题和未来发展趋势进行了总结和展望.
- 分子氧 /
- 活性氧物种 /
- 氧活化机理 /
- 新污染物 /
- 降解过程与路径
Abstract: In recent years, emerging contaminants (ECs) have been frequently detected in waters. ECs are chemically stable and easily bioaccumulative, thus seriously threaten the ecological environment and human health. To alleviate this problem, advanced oxidation process has been gradually developed into a promising remediation strategy. Among various oxidants, molecular oxygen is considered to be an abundant, economic and green oxidant. Molecular oxygen can be mainly activated into reactive oxygen species through catalytic electrons or energy transfer, which is expected to become a potential technology for removing emerging persistent contaminants in water. Currently, the research and development of more efficient catalytic materials (or other activation materials) for activating the molecular oxygen thoroughly and rapidly to degrade the ECs is the central goal of researchers. It mainly focuses on the basic concepts and latest progresses of molecular oxygen activation for degradation of ECs in water, including the main active oxygen species generated from molecular oxygen, the state-of-art activation strategy of molecular oxygen, examples of efficiently activation of molecular oxygen and degradation of ECs etc. Finally, the crucial problems and future development of molecular oxygen activation are summarized and prospected.
- molecular oxygen /
- reactive oxygen species /
- activation mechanism of molecular oxygen /
- emerging contaminants /
- degradation process and pathway

HTML全文

图 1 O₂活化机理示意^[7]

Figure 1. Molecular oxygen activation mechanism diagram^[7]

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图 2 氧化酶生物催化反应^[16]

Figure 2. Oxidase biocatalytic reaction^[16]

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图 3 Extrodial型儿茶酚双加氧酶中氧气与底物的活化机理^[18-21]

Figure 3. Dioxygen and substrate activation mechanism proposed in extrodiol catechol dioxygenase^[18-21]

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图 4 Introdial型儿茶酚双加氧酶中氧气与底物的活化机理^[22-24]

Figure 4. Substrate and dioxygen activation mechanism proposed in extrodiol catechol dioxygenase^[22-24]

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图 5 Fe²⁺/TPP体系中氯霉素降解路径^[74]

Figure 5. Proposed degradation pathway of CAP in Fe²⁺/TPP/ air system^[74]

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图 6 蒙脱土/亚纳米级零价铜体系中阿特拉津降解路径^[82]

Figure 6. Proposed degradation pathway of atrazine in the reaction system^[82]

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图 7 CuS₄团簇体系中降解四环素路径^[83]

Figure 7. Proposed degradation pathways of TC by ROS over CuS₄-ZIS^[83]

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图 8 TiO₂体系中降解PCB3路径^[84]

注：RT(retention time)为保留时间.

Figure 8. Proposed pathway for the photocatalytic degradation of PCB3 by TiO₂^[84]

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图 9 GO-TiO₂-Sr(OH)₂/SrCO₃体系降解菲路径^[86]

Figure 9. Proposed photocatalytic degradation pathway of phenanthrene by GO-TiO₂-Sr(OH)₂/SrCO₃ under solar irradiation^[86]

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表 1 部分水体ECs的浓度

Table 1. Concentrations of ECs in waters

新污染物	水体	浓度	数据来源
PPCPs	北京城市污水处理厂进水	52.3~4 490.5 ng/L	文献[70]
	厦门城市污水处理厂进水(醋氨酚)	2 963.5 ng/L
	英国城市污水处理厂进水(扑热息痛)	211.4 μg/L
EDCs	太湖	89.8~353.8 ng/L	文献[71]
	松花江	126.0~1 315.0 ng/L
	珠江	23.2~108.0 ng/L
PCBs	长江三角洲	1.23~16.6 ng/L (2009年)	文献[72]
	九龙江口	0.36~1 505 ng/L (1999年)
	东海	0.59~1.68 ng/L (2012年)
PAHs	长江武汉段	72.4~3 995.2 ng/g (2006年)	文献[73]
	黄河兰州段	960.0~2 940.0 ng/g (2005年)
	珠江广州段	1 433.6~10 810.5 ng/g (1997年)

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表 2 有关PPCPs的部分研究

Table 2. Some researches on PPCPs

材料	ROS	污染物	数据来源
纳米零价铜	·OH	恩诺沙星	文献[50]
亚铁离子/四聚磷酸	·O₂^-、·OH(主要)	氯霉素	文献[74]
Fe²⁺/三磷酸盐 (电Fenton反应)	·OH	阿米替林	文献[75]
超声/零价铁/磷酸三乙酯	·OH、·O₂^-、H₂O₂	诺氟沙星	文献[76]
铁强化的ZVAl/H⁺/空气	·OH	对乙酰氨基酚	文献[54]
零价铜	·OH、·O₂^-、H₂O₂	对乙酰氨基酚	文献[77]

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表 3 有关EDCs的部分研究

Table 3. Some researches on EDCs

材料	ROS	污染物	数据来源
零价铜	·O₂^-、H₂O₂、·OH	双酚A	文献[49]
零价铝-酸体系	H₂O₂、·OH	双酚A	文献[53]
亚铁-四聚磷酸配合物	·O₂^-、H₂O₂、 ·OH (主要)	洛克沙胂	文献[78]
铁丝-四聚磷酸钠-活性炭纤维 (电Fenton反应)	·O₂^-、H₂O₂、·OH	阿特拉津	文献[79]
Fe@Fe₂O₃纳米线/TPP	·O₂^-、H₂O₂、·OH	阿特拉津	文献[80]
零价铁-四聚磷酸盐	H₂O₂、·OH	五氯苯酚	文献[81]
蒙脱土/亚纳米级零价铜	·OH	阿特拉津	文献[82]
CuS₄团簇	·O₂^-、·OH	四环素	文献[83]

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表 4 有关PCBs、PAHs的部分研究

Table 4. Some researches on PCBs and PAHs

材料	ROS	污染物	数据来源
TiO₂	·OH、·O₂^-	4-氯联苯	文献[84]
生物炭负载P掺杂g-C₃N₄	·O₂^-	萘	文献[85]
氧化石墨烯-TiO₂-Sr(OH)₂/SrCO₃	·O₂^-、·OH	菲	文献[86]
氧化石墨烯/磷酸盐	·O₂^-、·OH	芘、菲、萘	文献[87]

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