Base Metal Nanostructures via Ionic-Liquid-based Synthesis (BaseMet-IL)

针对金属间化合物团簇和纳米颗粒，我们得到了高活性的羰基团簇(例如[BMIm]2[{PbMn(CO)5)}6I8]，{GeI3Fe(CO)3}2FeI4，(GeI3)2Fe(CO)4，Ge12{Fe(CO)3}8I4，[EMIM][Sn2I7Fe(CO)3]，[Co{1，4-C6H4(CN)2}2{NTf2}2][SnI{Co(CO)4}3]2)和金属间化合物纳米粒子(如Fe-Sn系，Co-Sn系，Ni-Ir系，Ni-Os系，Pd-Sn系，铂-Sn系)。我们还可以通过基于IL的直接合成或通过分解IL生成的羰基簇来显示双金属纳米颗粒的形成。除了详细的组成和结构表征外，我们还验证了各自的双金属纳米粒子的催化性能。离子液体的特殊性质(即氧化还原稳定性、热稳定性、弱配位性质)被证明是获得反应性羰基簇合物和双金属纳米粒子的关键。根据我们在第一个资助期的结果，我们现在将讨论基于离子液体的高活性和强亲氧贱金属纳米结构的合成。具体地说，我们将重点介绍钛、铌、硅和锗的类金属团簇和纳米颗粒。除了探索性的合成和基本的结构表征外，我们还将研究材料的性质，特别是包括量子尺寸效应和荧光(例如，对于Si，Ge，Si-Ge)以及基于加氢的催化性能(例如，对于双金属Ti-Pd，Ti-Pt，Nb-Pd，Nb-Pt系统)作为测试反应。针对Ti、Nb、Si、Ge等高活性亲氧贱金属，基于离子液体的合成在原理上似乎是理想的，但到目前为止还没有得到很好的解决。事实上，这种基于IL的策略可以提供一种新的、可靠的途径来获得高活性的贱金属纳米结构。

Aiming at intermetallic clusters and nanoparticles, we obtained highly reactive carbonyl clusters (e.g. [BMIm]2[{PbMn(CO)5)}6I8], {GeI3Fe(CO)3}2FeI4, (GeI3)2Fe(CO)4, Ge12{Fe(CO)3}8I4, [EMIm][Sn2I7Fe(CO)3], [Co{1,4-C6H4(CN)2}2{NTf2}2][SnI{Co(CO)4}3]2) and intermetallic nanoparticles (e.g. systems Fe-Sn, Co-Sn, Ni-Ir, Ni-Os, Pd-Sn, Pt-Sn) via IL-based synthesis. We could also show the formation of bimetallic nanoparticles via direct IL-based synthesis or via decomposition of IL-made carbonyl clusters. Besides detailed characterization of composition and structure, we have validated the catalytic properties of the respective bimetallic nanoparticles. The specific properties of the ILs (i.e. redox stability, thermal stability, weakly coordinating properties) turned out as essential for obtaining the reactive carbonyl clusters and bimetallic nanoparticles.Based on our results of the first funding period, we will now address the IL-based synthesis of highly reactive and strongly oxophilic base metal nanostructures. Specifically, we will focus on metalloid clusters and nanoparticles of Ti, Nb, Si and Ge. Besides the explorative synthesis and fundamental structural characterization we will study the material properties, especially including quantum-size effects and fluorescence (e.g. for Si, Ge, Si-Ge) as well as catalytic properties (e.g. for bimetallic Ti-Pd, Ti-Pt, Nb-Pd, Nb-Pt systems) based on hydrogenations as a test reaction. Aiming at highly reactive and oxophilic base metals such as Ti, Nb, Si and Ge, IL-based synthesis seems ideal in principal, but was barely addressed by now. In fact, such IL-based strategy could offer a new and reliable access to highly reactive base metal nanostructures.