配合物硫酸根自由基高级氧化体系的构建及去除有机微污染物研究

The so-called sulfate radical Advanced Oxidation Processes (SR-AOPs) are the most effective oxidation processes and are currently gaining significant importance in water treatment application. The present study found that the transition metal ions activated persulfate Advanced Oxidation Process can effectively degrade the typical environmental organic pollutants. But we still do not know the metal-ion complexes sulfate radical Advanced Oxidation Processes degradation of organic pollutants. Thus, in this study, stable transition metal complexes were form three categories complexing agent of inorganic, organic and natural, and the complexes were used to actived persulfate to build sulfate radical Advanced Oxidation Processes, and discussing the degradation possibility of three kinds of herbicides by the SR-AOPs. Understand the differences between the different transition metal complexes sulfate radical advanced oxidation degradation of environmental organic pollutants, this will lay the foundation for the complexes sulfate radical advanced oxidation process. The degradation intermediates of target compound were separated and identificated, and the quantum chemical calculations (frontier electron cloud density and transition state) were performed to predict the potential reaction sites and reaction energy barrier, so the general rule of sulfate radical degradation of the target were proposed base on the experimental and theoretical data. The acute toxicity of target and the degradation of intermediate solutions were evaluated at three different trophic levels, this will provide the scientific theory basis for this class of pollutants migration and transformation in actual water environment.

硫酸根自由基高级氧化法以其强氧化性的的特点已引起人们的广泛关注。目前研究发现，过渡金属离子活化过硫酸盐高级氧化法能够有效降解典型环境有机污染物，但是关于金属离子配合物硫酸根自由基高级氧化法降解有机污染物的研究尚不清楚。本研究拟选择无机、有机和天然三大类络合剂，探讨这些络合剂与过渡金属所形成配合物活化过硫酸盐降解3种除草剂的可能性，了解不同配合物硫酸根自由基高级氧化法降解目标物之间的差异，此将为配合物硫酸根自由基高级氧化法降解环境有机污染物奠定基础；对目标物的降解中间产物进行分离和鉴定，并结合对目标物的前线电子云密度和过渡态的理论计算数据，阐述硫酸根自由基降解目标物的一般规律；评价目标物及其降解中间产物的急性毒性随反应的时间的变化关系，为该类污染物的实际水体环境中的迁移和转化方面提供科学理论依据。

硫酸根自由基高级氧化法以其强氧化性的的特点已引起人们的广泛关注。但传统过渡金属离子活化过硫酸盐高级氧化法存在使用pH值范围窄，过渡金属离子难回收等问题。本项目选择了无机、有机和天然三类络合剂与过渡金属离子来构建配合物硫酸根自由基高级氧化法，本方法能够有效降解目标有机污染物，并扩宽了过渡金属离子活化过硫酸盐高级氧化法的应用范围。项目研究后期，均相的配合物硫酸根自由基氧化反应构建转向了非均相体系，所构建的非均相反应体系有效解决了金属离子污染的问题，同时起到了控制硫酸根自由基氧化反应作用范围。另外，对反应体系中活性物种进行间接的鉴定，通过一些现代分析测试手段对目标物产物进行鉴定，结合降解产物生态毒性数据，为该类环境污染物的环境转化归趋提供了一定的理论实验依据。