典型二噁英在气相与气-固界面微观降解机理的理论研究

项目名称： 典型二噁英在气相与气-固界面微观降解机理的理论研究

项目编号： No.21277082

项目类型： 面上项目

立项/批准年度： 2013

项目学科： 环境科学、安全科学

项目作者： 孙孝敏

作者单位： 山东大学

项目金额： 80万元

中文摘要： 本项目拟采用高精度的ab initio 量子化学方法和分子模拟技术，研究典型的二噁英物质在气相与气-固表面的降解过程，并与实验（如气相反应、气固界面催化反应等）结果相验证，从分子水平上阐明反应的微观机理。在量子化学的基础上进行动力学计算，获得反应速率常数、反应活化能等动力学信息，一方面可以为模式研究提供基本数据，另一方面可以计算各物质在环境中的寿命。通过量子化学计算还可以得到二噁英物质的分子结构参数，如：前沿分子轨道HOMO和LUMO轨道能量、能级差、原子电荷分布、构型参数等，结合动力学计算得到的反应速率常数等动力学信息，采用遗传算法和偏最小二乘法数值模拟，进行降解性能与结构之间的构效关系研究，构建二噁英类物质的降解性能预测模型。明确典型二噁英物质在气相与气-固表面中的微观降解机理，有助于更好地理解持久性有机污染物在大气环境中的反应活性和降解规律。

中文关键词： 典型二噁英；多相介质；量子化学与分子模拟；动力学性质；构效关系模型

英文摘要： Combining the experimental results of photolysis, chemical oxidation degradation, high level ab initio quantum chemistry method and molecular simulation have been used to study the heterogeneous degradation process of typical dioxin-like compounds in the gas phase and gas-solid surface, and to expound the reaction mechanism at the molecular level. Based on the quantum chemistry, the kinetic calculations have been carried out to obtain the kinetic information including the rate constants and activation energy. On the one hand, the information can provide basic data for model simulation. On the other hand, they can be used to calculate the lifetimes of the compounds in the environment. According to the quantum chemical calculation, we can also get the molecular structure parameters of the dioxin-like compounds, such as, the energies of the frontier orbitals (HOMO and LUMO orbital), energy level difference, atomic charge distribution and configuration parameters. Combined with the kinetic information of the rate constants, the numerical simulation of the genetic algorithm and partial least square method are used to research activity relationship between degradation performance and structure. Consequently, the prediction model for degradation performance of the dioxin-like compounds is built and the practical applic

英文关键词： Typical Dioxins；Gas Phase and Gas-solid Interface；Quantum Chemistry and Molecular Simulation；Dynamics Property；Quantitative Structure Activity Relationship