Synthesis of Noble Metal-oxo Cluster-based Metal-Organic Frameworks and their Use in Heterogeneous Catalysis and Magnetism

基于贵金属氧簇的金属有机框架的合成及其在多相催化和磁性中的应用

• 批准号: 448088997
• 负责人: Professor Ulrich Kortz, Ph.D.
• 金额: --
• 依托单位: Universitat Rovira i Virgili
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/448088997?language=en
• 关键词: Synthesis; Noble; Metal; oxo; Cluster

This project aims at the systematic design, synthesis and characterization of a series of fundamentally novel polyoxo-noble-metalate (PONM)-based metal-organic frameworks (MOFs) and the investigation of their catalytic and magnetic properties. The entire class of discrete polyoxopalladates (POPs) and polyoxoaurates (POAs) of different shape, size and composition will be utilized to construct noble-metal and mixed noble-metal-based PONM-MOFs. The stability and composition of such framework materials will be tuned by suitable modification of the organic linkers, or by employing a dual secondary-building-unit (SBU) strategy, wherein the POP/POA SBUs will be linked to other types of SBUs such as conventional POMs, noble-metal complexes or single metal-ions. This project is expected to result in a library of PONM-MOF-based heterogeneous catalysts with either single or dual catalytic centers, which will be utilized as catalysts for organic oxidation, reduction, and C-C coupling reactions. The obtained PONM-MOFs can also be used as sacrificial templates to synthesize noble-metal- or mixed-noble-metal-based nanoparticles@porous-carbon composites, which will be tested as catalysts for photo- and electrocatalytic reactions. The formation of noble-metal-based nanoparticles from PONM-MOFs is highly attractive, because the composition and size of the nanoparticles can be tuned by simply using PONMs of different shape, size and composition as SBUs. We also aim to utilize lanthanide-centered POPs as SBUs to isolate Ln-POP-MOFs and to study them as molecular spin qubits, because the individual lanthanide ions inside the POP cavities exhibit highly symmetrical coordination environments (8-coordinated cubic in the LnPd12 nanocube or 10-coordinated pentagonal-prismatic in the LnPd15 nanostar). The Ln-POPs are well-oriented in the rigid framework of the Ln-POP-MOFs and the interactions of the individual spin qubits with each other can be fine-tuned by increasing/decreasing the length of the organic linkers or by using flexible organic linkers. The proof of principle for the synthesis, structure and catalysis of POP-MOFs was demonstrated recently (J. Am. Chem. Soc. 2019, 141, 3385−3389).

本项目旨在系统地设计、合成和表征一系列基于多氧贵金属（PONM）的金属有机框架（MOFs），并研究其催化和磁性。不同形状、尺寸和组成的整个类别的离散的多钯酸盐（POP）和多金酸盐（POA）将被用于构建基于贵金属和混合贵金属的PONM-MOFs。这种骨架材料的稳定性和组成将通过有机连接体的适当修饰或通过采用双次级结构单元（SBU）策略来调节，其中POP/POA SBU将连接到其它类型的SBU，例如常规POM、贵金属络合物或单金属离子。该项目预计将产生具有单或双催化中心的PONM-MOF基非均相催化剂库，其将用作有机氧化，还原和C-C偶联反应的催化剂。所获得的PONM-MOFs也可以用作牺牲模板来合成基于贵金属或混合贵金属的纳米颗粒@多孔碳复合材料，其将被测试作为光催化和电催化反应的催化剂。由PONM-MOF形成基于贵金属的纳米颗粒是非常有吸引力的，因为可以通过简单地使用不同形状、尺寸和组成的PONM作为SBU来调节纳米颗粒的组成和尺寸。我们还旨在利用镧系元素为中心的POP作为SBU来隔离Ln-POP-MOFs并将其作为分子自旋量子比特进行研究，因为POP腔体内的单个镧系元素离子表现出高度对称的配位环境（LnPd 12纳米立方体中的8配位立方或LnPd 15纳米星中的10配位五边形棱柱）。Ln-POP在Ln-POP-MOFs的刚性框架中具有良好的取向，并且可以通过增加/减少有机连接体的长度或通过使用柔性有机连接体来微调各个自旋量子比特彼此的相互作用。最近证明了POP-MOF的合成、结构和催化的原理证明（J. Am. 2019，141，3385 - 3389）。