Double salts with a multifunctional character made from Zintl phases and oxo- as well as halogeno-metalates

由 Zintl 相和氧代以及卤代金属盐制成的具有多功能特性的复盐

• 批准号: 508247931
• 负责人: Professor Dr. Thomas F. Fässler
• 金额: --
• 依托单位: Lehrstuhl für Anorganische Chemie mit Schwerpunkt Neue Materialien
• 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/508247931?language=en
• 关键词: Double; salts; multifunctional; character; made

This research project aims for the development of fundamental compounds for new functional materials by means of synthetic solid-state chemistry through the combination of two inorganic components at the molecular ionic level. The focus is on deltahedral, polyanionic germanium and tin clusters comprising nine atoms, that are in combination with a second type of anion such as oxometalates and metal-halide anions form new, hybrid semiconducting solid state materials (double salts). Due to their mutual structural tunability, the combination of both alkali-metal Zintl phases and alkali-metal metal-oxides or metal-halides offers numerous possibilities for the generation and design of new multi-component hybrid materials. Since double salts can appear with variable composition, this compound class has the potential for tunable band gaps. The new material class has application potential in optoelectronics and, in principle, also as a water splitting catalyst.In a first step, synthesis protocols for double salts are systematically developed based on the few known representatives and are applied to various other combinations. The new compounds are structurally characterized by means of X-ray diffraction methods and Raman spectroscopy. Basic electronic properties such as band gaps or magnetic properties, oxidation states of the constituting elements that suggest a possible charge transfer between the units, are determined experimentally. Using quantum chemical calculations, on the one hand, the electronic structures and band gaps are calculated. On the other hand, stable, new, unknown candidates with hybrid character are identified on the basis of structural relationships and tested with regard to thermodynamic stability using theoretical methods. In a further step, selected candidates are specifically synthesized using the synthesis protocols developed. Specifically, in the project applied for here, hybrid compounds are produced which contain the polyanions [Ge9]4–, [Sn9]4– and [M@Sn9] x– as component 1 and metal-oxide or metal-halide anions of the [MO4]x– (M = transition metal) or tetrahedrally coordinated halides (e.g. [SnBr4]2–, [PbBr4]2–, [MX4]x-; X = halogen) or halides of the type [MX6]x- (M = Sn, Pb) as component 2. The structural units of both components are known as alkali-metal compounds, however in combination they are systematically developed here for the first time. Component 2 is already used today in metallic bronzes and in solar cells. The combination enables charge-transfer processes between the building units of the components and better tunable band gaps.

该研究项目的目的是通过在分子离子水平的两个无机成分结合结合合成固态化学来开发新功能材料的基本化合物。重点放在三角洲，聚苯乙烯也和锡簇上，其中包括九个原子，它们与第二种阴离子（例如氧盐和金属壁阴离子）结合使用，形成了新型的混合半导体固态材料（双盐）。它们相互的结构可可匹配性，碱金属相和碱金属氧化物或金属 - 甲板的组合为新的多组分混合材料的生成和设计提供了许多可能性。由于双盐可以带有可变成分，因此该化合物具有可调频带间隙的潜力。新材料类具有光电子的应用潜力，原则上也是作为水分分裂催化剂的应用。在第一步中，双盐的合成方案是根据少数已知代表系统地制定的，并应用于其他各种组合。新化合物在结构上通过X射线衍射方法和拉曼光谱法进行了特征。基本的电子特性，例如带隙或磁性特性，构成元素的氧化态，这些元素表明单位之间可能的电荷转移，是通过实验确定的。一方面，使用量子化学计算计算电子结构和带隙。另一方面，根据结构关系确定具有混合特征的稳定，新的，未知的候选者，并使用理论方法对热力学稳定性进行了测试。在另一个步骤中，使用开发的合成协议专门合成选定的候选者。具体而言，在此处适用的项目中，产生了杂种化合物，其中包含聚会[GE9] 4-，[SN9] 4-和[M@Sn9] X-作为成分1，以及[Mo4] X –（M = MON）X –（M =过渡金属）或四面体共同的Halides Halides Halides（E.G. E.G. Snbr4）的金属 - 氧化物或金属 - 甲烷阴离子（ [mx4] x-; x =卤素）或类型[Mx6] X-（M = SN，Pb）作为组件2。这两个组件的结构单元被称为碱金属化合物，但是在这里首次系统地开发了它们。今天已经在金属青铜器和太阳能电池中使用了组件2。该组合可以在组件的建筑单元和更好的可调频带差距之间进行电荷转移过程。