水中有机磷阻燃剂与•OH和SO4•-反应动力学及机制的实验和计算模拟研究

探究羟基自由基(•OH)和硫酸根自由基(SO4•-)参与的高级氧化技术去除水中新型污染物有机磷阻燃剂(OPFRs)对其污染预防和控制具有重要意义。然而，OPFRs结构及种类众多，目前绝大多数的OPFRs与•OH和SO4•-反应的动力学参数未有报道，反应机制和产物也尚不清楚。因此，本项目拟采用实验测定、定量构效活性关系(QSAR)和量子化学计算相结合的方法，构建科学有效地预测OPFRs与•OH和SO4•-反应速率常数的QSAR模型；基于量化计算发展OPFRs与•OH和SO4•-反应速率常数、反应途径和产物的预测方法；探讨分子结构参数对反应活性的影响；揭示具有不同取代基和取代模式的OPFRs与•OH和SO4•-反应的机制。本项目可为预测OPFRs类污染物在城市污水、饮用水等处理过程中及在自然环境中的转化产物和速率提供基本工具，同时为该类污染物的生态风险评价以及管理政策的制定提供科学依据。

It is of great significance for their pollution prevention and control to investigate the advanced oxidation processes involved in hydroxyl radical (•OH) and sulfate radical (SO4•–) for removing the emerging pollutants organophosphorus flame retardants (OPFRs) in water. There are a large number of OPFRs with different structures, however, the kinetics parameters for most OPFRs reaction with •OH and SO4•– have never been reported, and the underlying reaction pathways and products remain unclear. Thus, by employing the experimental determination, quantitative structure activity relationship (QSAR) and quantum chemistry calculation methods, in this project two QSAR models for predicting reaction rate constants of OPFRs with •OH and SO4•– will be constructed respectively; based on the quantum chemistry calculation, methods for predicting reaction rate constants, reaction pathways and products of OPFRs with •OH and SO4•– will be established respectively; the effect of molecular structure parameters on the reaction activity will be investigated; and the reaction mechanism of OPFRs which have different substituents and substitution patterns with •OH and SO4•– will be unveiled. This project can provide a foundational tool for predicting the transformation products and rates of OPFRs during the treatment process in municipal sewage, drinking water and in environment, meanwhile provide the scientific basis for ecological risk assessment and the formulation of management policies of OPFRs.