Porous Alkali-Metal-Organic Frameworks – From Synthesis Towards Application

金属-有机骨架(MOF)是一类纳米多孔、无机-有机配位化合物，在开发资源和能源高效的技术过程和应用(如催化、碳捕获、气体分离和传感)方面具有巨大的潜力。这些配位化合物通常由过渡金属离子构成，这些过渡金属离子通过有机连接物相互连接，以生成多孔骨架结构。然而，基于碱金属离子的MOF极其罕见。这可能是因为碱性离子的配位化学(配位数和几何构型)多变且难以预测，这使得靶向结构设计变得困难。然而，多孔碱金属有机材料在电池技术中提供了巨大的应用潜力，从基础配位化学的角度进一步引起了人们的极大兴趣。在这个项目中，我们想要探索这种多孔碱金属有机材料，以部分缩小与成熟的传统碱金属有机材料的差距，后者是由后面基团的金属离子构建的。在非常有希望的初步结果的基础上，我们希望开发一个概念，通过特定的连接子设计来定向合成健壮的、等网状的、基于羧酸盐的钠-MOF。除了用X射线衍射、热重分析、气体吸附和光谱等手段对这些新型材料进行详细的表征外，我们还想进一步评估这些钠-MOF作为钠离子电池电极材料和作为固体电解液的应用潜力。战略目标：-开发第一系列具有不同孔径、体积和功能的等网状钠-MOF。-评估钠-MOF作为钠离子电池活性电极材料的应用。-开发一种简单有效的多孔钠-MOF的机械力化学合成路线。-分析这些材料的离子导电性，并通过有针对性地实施晶格缺陷来改善其导电性。-将合成概念从钠-MOF转移到其他碱-MOF。

Metal-organic frameworks (MOFs), a family of nanoporous, inorganic-organic coordination compounds, promise great potential for the development of resource and energy efficient technological processes and applications (e.g. in catalysis, carbon capture, gas separation and sensing). These coordination compounds are typically constructed from transition metal ions, which are interconnected by organic linkers, to generate porous framework structures. MOFs based on alkali metal ions are extremely rare, however. This may be reasoned in the variable and less predictable coordination chemistry (coordination number and geometry) of alkali ions, which makes targeted structure design difficult. Porous alkali-metal-organic materials, nevertheless, offer great potential for applications in battery technology and are further of great interest from the viewpoint of fundamental coordination chemistry.In this project, we want to explore such porous alkali-MOFs to partially close the gap to the well-established conventional MOFs, which are constructed from metal ions of the later groups. On the basis of very promising preliminary results, we want to develop a concept for the targeted synthesis of robust, isoreticular, carboxylate-based sodium-MOFs via specific linker design. Besides the detailed characterisation of these novel materials with X-ray diffraction, thermogravimetry, gas sorption and spectroscopic methods, we further want to evaluate the potential of these sodium-MOFs for applications as electrode materials for sodium ion batteries and as solid electrolytes. Strategic objectives: - Development of the first series of isoreticular sodium-MOFs with variable pore sizes, volumes and functionalities. - Evaluation of sodium-MOFs for applications as active electrode materials for sodium ion batteries.- Development of a facile and efficient mechanochemical synthesis route for porous sodium-MOFs.- Analysis of the ionic conductivity of these materials and improvement of their conductivity via targeted implementation of lattice defects.- Transfer of the synthesis concept from sodium-MOFs to other alkali-MOFs.