环境内分泌干扰物的选择性去除和机制研究

Abstract: Since the environmental endocrine disrupting chemicals (EDCs) possess the characteristics of low concentration, high toxicity and abundant variety, while large diversity for those with different structure, but big sameness for those with similar structure, how to carry out the selective removal of EDCs is of great significance and has become a hot and difficult topic in water environment fields in recent years. This project proposes the shape selective recognition method based on highly ordered single crystal surface modified with molecular imprinting sites, in order to achieve high efficiency and highly selective photoelectrocatalytic (PEC) integrated removal of EDCs. This method skillfully combines the photocatalysis, electrocatalysis, and shape-selective catalysis on the same surface of electrode with controllable and regular single crystal structure. This method not only possesses high PEC degradation efficiency, but also has high selectivity. Based on the above investigation, this project will further explore the selective degradation method with multiple molecular imprinting sites and recognition ability for simultaneously removing EDCs in the same category but with different structure. Meanwhile, the specific adsorption of EDCs on the molecular imprinting surface of single crystal, the catalytic activation of EDCs, as well as the key mechanism for selective bond cleavage will be deeply investigated in molecular level by means of in-situ spectroscopy and PEC method. The specific interaction between the molecular imprinting sites and the typical EDCs, and the mechanism of selective recognition will also be elaborated at the level of microscopic interface structure, including the structure of terminal functional groups, steric hindrance effect, semiconductor band gap structure of PEC catalyst, and the characteristics of electron transfer. Finally, the kinetics and mechanism for selective removal of EDCs will be analyzed.

环境内分泌干扰物EDCs浓度低、毒性大、种类多、结构繁杂，如何选择性高效去除，是水环境化学研究热点和难点。项目提出基于有序单晶光电催化表面高印迹表达的择形识别技术，构建选择性光电一体化催化降解新方法，实现EDCs的高效去除。该方法将光催化、电催化和择形催化巧妙发生在可控、规整、单晶结构的同一表面上，增强光电催化效率的同时，赋予方法的高选择性，并可设计引入多重分子印迹识别的协同功能，同步去除水中同一类EDCs。采用原位光谱、波谱光电研究等方法，从分子水平上揭示降解过程中EDCs分子在单晶印迹表面的特征吸附、分子活化、加羟基过程、瞬态物种、竞争反应和选择性断键的关键机制，从表面终端结构、印迹位点化学微环境、超分子识别成键特性、空间位阻效应、能带结构和电子转移等界面微观结构层次上，阐明EDCs分子与催化表面印迹位点的特殊相互作用机理和选择性机制；明晰各种典型EDCs分子反应机理和去除动力学过程。

水中环境内分泌干扰物（EDCs）浓度低、毒性大、种类多、共存污染体系复杂，如何实现选择性高效去除，是环境水处理的国际前沿课题。本项目围绕EDCs的选择性去除新方法、光电催化分子转化机理以及选择性机制等若干关键科学问题，开展了系统深入研究，取得了以下代表性成果：. （1）创新发展出选择性去除水中有毒有害有机特征污染物的光电催化新方法。构建了基于1D和2D有序单晶表面分子印迹功能识别、表面化学键作用识别、晶面酸碱配位作用识别、伪模板分子印迹识别等多种选择性光电催化降解方法，实现了酚类（苯酚、壬基酚、双酚A等）、雌激素类（17β-雌二醇等）、酞酸酯类（邻苯二甲酸二酯一种和一类）、含硫或卤代污染物（硫酚、多氯联苯、阿特拉津）等典型EDCs痕量和超痕量的选择性去除。处理后目标EDCs可低至µg/L甚至ng/L。. （2）利用原位（红外、拉曼）光谱、电子顺磁共振波谱（ESR）与光电化学联用等手段，结合瞬态吸收光谱、同位素标记等多种先进技术，阐明了光电一体化协同氧化的原理，揭示了EDCs污染分子与光电催化表面的相互作用和选择性机制。发现单晶表面构筑的分子印迹显著减少了表面非特征吸附，增强了印迹作用识别能力，并活化了污染分子C-H、C-X等化学键，使其更易被羟基自由基进攻，得以选择性高效光电催化降解。. （3）引入核酸适配体对靶向目标具有特异性识别的基因技术，构筑出简便、专一性强的雌二醇、双酚A、邻苯二甲酸二甲酯、PCB、阿特拉津等近十种典型 EDCs光电化学传感器，可用于跟踪检测 EDCs 去除动力学过程。 . 已发表标注本项目资助的SCI论文74篇，包括Energy Environ. Sci. 1篇、Angew. Chemie 1篇、Adv. Mater. 1篇、Chem. Soc. Rev. 1篇和 Environ. Sci. Technol. 5篇等；申请国家发明专利34项，已授权国家发明专利12项。项目培养了优青1人、上海领军人才1人、博士后2人、博士和硕士毕业研究生18人。项目成果可为城市污水厂实际复杂水体中低浓度EDCs去除应用提供关键技术和基础理论指导。