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

针对金属间团簇和纳米粒子，我们通过il基合成获得了高活性羰基团簇（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）和金属间纳米粒子（如Fe- sn、CO - sn、Ni-Ir、Ni-Os、Pd-Sn、Pt-Sn）。我们还可以通过直接基于白介素的合成或通过分解白介素制造的羰基簇来形成双金属纳米颗粒。除了详细表征组成和结构外，我们还验证了各自双金属纳米颗粒的催化性能。ILs的特定性质（即氧化还原稳定性、热稳定性、弱配位性）被证明是获得活性羰基簇和双金属纳米颗粒的必要条件。基于我们第一个资助期的结果，我们现在将解决基于il的高活性和强亲氧性贱金属纳米结构的合成。具体来说，我们将重点研究钛、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，我们将研究材料的性质，特别是包括量子尺寸效应和荧光（例如Si， Ge, Si-Ge）以及基于加氢反应的催化性质（例如双金属Ti-Pd， Ti-Pt, Nb-Pd， Nb-Pt体系）作为测试反应。针对高活性和亲氧性贱金属，如Ti， Nb， Si和Ge，基于il的合成在原则上似乎是理想的，但现在几乎没有解决。事实上，这种基于il的策略可以为高活性贱金属纳米结构提供一种新的可靠途径。

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.