表界面反应的多尺度密度泛函研究

The project addresses the surface and interface reactions. Towards a deep understanding of the relation among reactant concentration (mass transfer effect), inhomogeneous solvent structure (surface/interface effects) and reaction mechanism, we aim to develop a reaction density functional theory (DFT) by incorporating quantum DFT with classical DFT. The proposed theory is supposed to provide a multi-scale description for the interaction between quantum subsystem and its classical environment. Similar to QM/MM method, reaction DFT combines two theories individually for the systems at different length scales, and in particular quantum DFT treats the intrinsic reaction in terms of the electron density while classical DFT deals with liquid environment via the local molecular density. The coupling between the systems of two length scales is characterized by the great impact on the value of reaction activation energy from the surrounding and also by the modification of microscopic solvent structure from the reaction. By employing the constructed reaction DFT with the supplementary of computer simulation, we thereafter investigate several important chemical reactions in the vicinity of solid-liquid surface or liquid-liquid interface, and explore the relations between the reaction path and the reaction conditions including reactant concentration, characteristic of reaction medium and solvent structure etc.. Those relations are revealed from three length scales ranging from molecular scale to interfacial scale and finally to meso-sacle. The particularity and universality of those surface/interface reactions should be summarized. The success of this project will provide solid support and theoretical guidance for the development of multiphase transfer and reaction process intensification techniques.

本项目针对表界面反应，围绕反应介质浓度(传递效应)、表界面微观结构(表界面效应)和反应机制的相互关系，通过结合不同描述精度的量子密度泛函和经典密度泛函，构建多尺度的反应密度泛函理论，发展研究量子系统与经典系统耦合的新方法。与量子力学/分子力学方法(QM/MM)思想类似，在反应密度泛函框架下，本征反应和反应介质分别用两个尺度的理论来处理，其中本征反应用量子密度泛函描述，而反应介质响应则用经典密度泛函研究。两个尺度之间的相互作用体现在反应介质对本征反应路径的影响以及反应对表、界面系统微观结构的改变。应用反应密度泛函理论并结合计算机模拟，我们继而研究化学工程中若干重要的表界面反应，在分子、表界面、分子群三个尺度上揭示反应路径与反应物浓度、介质特性、表界面结构等的相互关系, 归纳表界面反应机理的一些共性与特性，从而为多相传递和反应过程强化技术的开发提供理论指导。

本项目针对表界面反应，围绕反应介质浓度(传递效应)、表界面微观结构(表界面效应)和反应机制的相互关系，通过结合不同描述精度的量子密度泛函和经典密度泛函，构建多尺度的反应密度泛函理论，发展研究量子系统与经典系统耦合的新方法。继而应用反应密度泛函理论并结合计算机模拟，研究化学工程中若干重要的表界面反应，在分子、表界面、分子群三个尺度上揭示反应路径与反应物浓度、介质特性、表界面结构等的相互关系, 归纳表界面反应机理的一些共性与特性，从而为多相传递和反应过程强化技术的开发提供理论指导。在项目执行期间，项目组紧紧围绕课题的研究目标，按计划开展具体研究，取得了较大的研究突破，共发表SCI论文23篇, EI论文2篇，申请专利３项(２项已授权)。发表的论文其中包括Science子刊1篇，Nature子刊1篇，其它一区论文３篇, 化工三大期刊论文４篇。项目负责人受邀参加国际国内会议20余次，其中Keynote 报告4次。发展界面反应调控模型与多尺度研究方法，可为工艺的优化与开发提供理论指导，从而带来极大的社会效应和潜在的经济价值。