基于金属有机骨架的复合体系中电子态行为的理论模拟研究

项目名称： 基于金属有机骨架的复合体系中电子态行为的理论模拟研究

项目编号： No.21473166

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 江俊

作者单位： 中国科学技术大学

项目金额： 85万元

中文摘要： 金属有机骨架（metal-organic framework: MOF）材料具有多样性和易功能化等优点，其复合体系可实现许多重要应用。但MOF的非严格周期结构和局域量子态等复杂性，及材料复合的复杂表界面问题，导致构效关系和微观过程协同原理不清晰，造成其在光催化等领域的应用瓶颈。 项目基于微观角度，将MOF复合体系复杂的工作过程，归结为在独特空间与电子结构下电子态的形成、耦合和演化行为这一单一主线。聚焦于几个典型MOF与重要半导体、金属的复合结构的光催化应用，发展和应用计算化学的多尺度模拟方法，结合量子化学、固体物理、分子力学和经典电动力学模型，以第一性原理精度描述MOF这类具有非严格周期性的大尺度复杂体系，揭示其关键电子态形成、量子态耦合、物理与化学变化等行为，模拟其性质对材料组成、形貌、晶相、杂质和缺陷等因素的依赖关系，寻找适用于高效光催化和光电材料等的构效关系，设计实用复合体系。

中文关键词： 量子化学计算；多尺度模拟；电子态；金属有机骨架；光催化

英文摘要： There is an important trend towards material design and utilization based on composite system. Metal-organic framework structure, owing to its advantages of high degree of diversity and tunability, is widely used to form composite materials with semiconductor, metal, molecule, and so on. MOF-based composite systems have been extensively investigated, exhibiting a great range of chemical and physical properties useful for important applications such as gas storage, catalysis and luminescence. However, the complexity of MOF structures, and the difficulty to control the complicated surfaces and interfaces in MOF-based composite systems, have impeded people from fully understanding the structure-property relationship as well as the synergetic effect of multiple processes. This has become the bottleneck for their realistic utilizations. The proposed project aims at developing and applying first-principles based multiscale modeling methods, to study the formation, coupling and evolution of electronic state in MOF-based composite system. This will convert the complicated modeling of various functions in complex systems, to the same type of simulation of electronic state behavior. We will focus on several typical MOF structures, in combining with some widely used semiconductors or metal nanocrystals, to investigate their photocatalysis and luminescence mechanisms. Theoretical methods including quantum chemistry, solid state physics, molecular mechanics, and classical electrodynamics will be combined to study the semi-periodical and large scale complex systems, to reveal the formation of electronic states, coupling of quantum states, and physical and chemical conversions. These information could lead to a clear understanding of the property dependence on key material parameters such as composition, crystal phase, morphology, impurity, defect, which will eventually help us to design practically efficient MOF-based composite systems for important applications.

英文关键词： quantum chemistry computation;multiscale modeling;electronic state;metal-organic framework;photocatalysis