Redox-Active Metal-Organic Frameworks: Novel Entatic State Catalysts?

氧化还原活性金属有机框架：新型熵状态催化剂？

• 批准号: 202904373
• 负责人: Professor Dr. Karsten Reuter
• 金额: --
• 依托单位: Lehrstuhl für Festkörperchemie
• 依托单位国家: 德国
• 项目类别: Priority Programmes
• 财政年份: 2011
• 资助国家: 德国
• 起止时间: 2010-12-31 至 2015-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/202904373?language=en
• 关键词: Redox; Active; Metal; Organic; Frameworks

Porous, redox-active metal-organic frameworks (MOFs) shall be developed which are constructed from aromatic N-donor ligands (e.g. pyrazolate or triazolate moieties) and openshell 3d transition metal ions. Previous investigations have demonstrated that the use of heterocyclic aromatic N-donors leads to greatly enhanced hydrolytic stability of the MOF compounds, which is a necessary condition for catalytic oxidation processes. Particular attention will be addressed to the specific advantages of embedding a multinuclear transition metal cluster into a rigid 3D coordination framework (“entatic state catalyst”). Thus, the spectroscopic and catalytic properties of solid MOF catalysts shall be compared with special emphasis laid upon gas phase reactions. Quantum chemical investigations will address different oxidation states of the electronically coupled metal sites in multinuclear clusters, and their role in catalytic oxidation or oxygenation cycles. Density functional theory (DFT) based on general gradient approximation (GGA) and hybrid functionals is applied to investigate ground and excited state properties of the MOFs. Special attention will be paid to important properties like vibrational and UV/VIS spectroscopy as well as to the redox behaviour of the envisaged compounds.

应开发由芳香族n-二位酮配体（例如吡唑酸盐或三唑盐部分）和OpenShell 3D过渡金属离子构建的多孔，氧化还原活性金属有机框架（MOF）。先前的研究表明，使用杂环芳香族N谱系会导致MOF化合物的水解稳定性大大增强，这是催化氧化过程的必要条件。将特别注意将多核过渡金属群集嵌入刚性3D协调框架（“诱导状态催化剂”）的特定优势。这是将固体MOF催化剂的光谱和催化特性与对气相反应的特别重点进行比较。量子化学研究将解决多核簇中电子耦合金属位点的不同氧化态，以及它们在催化氧化或氧合周期中的作用。基于一般梯度近似（GGA）和杂交功能的密度功能理论（DFT）用于研究MOF的地面和激发态特性。将特别注意重要特性，例如振动和紫外线光谱，以及所设想化合物的氧化还原行为。