水体中邻苯二甲酸酯降解机理的量子化学及蒙特卡洛模拟

项目名称： 水体中邻苯二甲酸酯降解机理的量子化学及蒙特卡洛模拟

项目编号： No.21477065

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 化学工业

项目作者： 何茂霞

作者单位： 山东大学

项目金额： 86万元

中文摘要： 邻苯二甲酸酯(PAEs)是一类全球普遍存在的有机污染物。已有六种被美国EPA列为优先控制污染物，三种被我国国家环保局列为优先监测污染物。PAEs的生物暴露表现出了神经毒性和生殖异常，属于环境内分泌干扰物。PAEs的环境转化过程已成为环境化学亟待解决的科学问题。本项目拟以典型PAEs为研究目标，基于量子化学计算和蒙特卡洛模拟相结合的方法对其在水体中降解过程的微观反应机制进行研究。通过量子化学计算从理论上定量给出化学转化过程中各驻点的结构参数和振动频率；反应过程中各基元反应的活化能、反应焓及吉布斯自由能变等热力学参数；在此基础上计算各反应速率和反应分支比，比较不同条件下PAEs的降解效率。通过蒙特卡洛模拟定量给出溶剂存在时PAEs降解过程的各热力学参数和微观反应机理。期望本项目的开展能够揭示PAEs在水体中发生降解的微观机制，为污染物的水处理过程提供理论数据参考。

中文关键词： 邻苯二甲酸酯；降解机理；水溶液；量子化学计算；蒙特卡洛模拟

英文摘要： Phthalate esters(PAEs)are a class of organic compounds that are universally existed in the world. There are six PAEs have been listed as a category of priority control pollutants by the U.S. Environmental Protection Agency(US EPA) and three PAEs are classified as priority detect pollutants by the China National Environmental Monitoring Center. PAEs,as endocrine disruptors,show neurotoxicity and reproduction abnormality. It is desirable to study the environmental transfromation processes of PAEs. In this proposal, several classical PAEs are selected as models to investigate the degradation mechanisms of PAEs in aqueous solution using Quantum Chemical Calculation method and Monte Carlo simulations. The geometrical parameters and vibrational frequencies of the reactants, intermediates, transittion states and reaction products located on the reaction processes will be given out quantitively through thermaldynamic parameters such as active energies, enthalpies and Gibbs free energies will also be obtained. The total and individual reaction rate constants can be calculated on the basis of above thermaldynamic parameters and then the branch ratios will be postulated. Through Monte Carlo Simulations, the detailed degradation mechanisms of PAEs in aqueous solution are expected to be revealed. Some original innovative data about reaction processses and kinetics of PAEs in water will be gained which can provide reliable proofs for water treatment.

英文关键词： Phthalate Acid Esters;Degradation Mechanism;Aqueous Solution;Quantum Chemical Computation;Monte Carlo