Oxide Nanostructures

有机分子功能化的自组装纳米粒子系统和纳米晶光电极是具有技术影响的功能特性的杂化纳米材料的重要例子。该项目旨在控制金属氧化物/有机分子结构的杂化制造，达到纳米尺度。通过这种方法，funCOS 5项目解决了整个联盟的一个主要目标，即氧化物表面分子膜的功能景观。相应的氧化物纳米结构作为互补的funCOS模型系统将通过反映funCOS 5合作伙伴的特定专业知识的各种技术来制造。主要的方法有：在金属氧化物薄膜上吸附功能分子，特别是卟啉；利用聚焦电子束局部解离适当的前驱体或在特高压下纳米光刻法激活氧化物载体；化学气相合成氧化物纳米颗粒；在电解质溶液中自组织阳极纳米结构生长。我们将建立稳健的合成和生长方案，以生成可变组成复杂性的负载和非负载氧化物纳米结构。这些将包括从过渡金属氧化物（CoO）掺杂的宿主氧化物（MgO）到复合材料和CoOx-TiO2超晶格状纳米管结构。我们将讨论结构的形成及其对不同长度尺度的吸附和反应性的影响。因此，该结构将被优化为作为吸附卟啉分子的模板，以产生具有特定性质的杂化材料。在有或没有支撑底物的情况下，卟啉的吸附行为及其在不同长度尺度上的组织将揭示结构和材料的特定因素，这些因素将能够平衡分子-底物和分子-分子相互作用。特定的局部相互作用之间的特征氧化物表面特征（如角落，边缘，热和电子束诱导的氧空位）和有机连接和/或卟啉将被解决。由此产生的模型结构将使我们能够将2D表面（funCOS 1-3）表面科学研究的见解与3D混合纳米结构联系起来。此外，我们将阐明剩余水分子和羟基对纳米结构稳定性的影响，ii)对卟啉和官能团的吸附的影响，以及iii)对最终功能性能的影响。与funCOS 1-4和6的密切合作将使我们能够将表面科学技术在原子清洁、单晶表面上获得的原子尺度见解转移到具有可变结构和成分复杂性的2D纳米结构模板和3D高表面积材料上。

Self-assembled nanoparticle systems and nanocrystalline photoelectrodes that are functionalized with organic molecules are key examples of hybrid nanomaterials with functional properties of technological impact. This project aims at the controlled fabrication of hybrid metal oxide/ organic molecule structures down to the nanometer scale. With this approach the funCOS 5 project addresses one major goal of the whole consortium, which is the functional landscaping of molecular films on oxide surfaces. The corresponding oxide nanostructures as complementary funCOS model systems will be fabricated by a variety of techniques reflecting the specific expertise of the funCOS 5 partners. The main methods are: adsorption of functional molecules, in particular porphyrins, on thin metal oxide films, an approach in which a focused electron beam is employed to locally dissociate an appropriate precursor or to nanolithographically activate oxide supports in UHV, chemical vapor synthesis of oxide nanoparticles and self-organized anodic nanostructure growth in electrolyte solution. We will establish robust synthesis and growth protocols for the generation of supported and unsupported oxide nanostructures of variable compositional complexity. These will range from transition metal oxide (CoO) doped host oxides (MgO) to composites and CoOx-TiO2 superlattice-like nanotubular structures. We will address structure formation and its impact on adsorpion and reactivity on different length scales. Thereby, the structures will be optimized to act as templates for the adsorption of porphyrin molecules to yield hybrid materials with specific properties.With and without supporting substrates, the adsorption behavior of the porphyrins and their organization at different length scales will reveal structure and materials specific factors that will enable to balance molecule-substrate and molecule-molecule interactions. Specific local interactions between characteristic oxide surface features (e.g. corners, edges, thermally and electron beam induced oxygen vacancies) and organic linkers and/ or porphyrins will be addressed. Resulting model structures will enable us to link insights from surface science studies on 2D surfaces (funCOS 1-3) to 3D hybrid nanostructures. Moreover, we will elucidate the impact of residual water molecules and hydroxyls i) on nanostructure stability, ii) on the adsorption of porphyrins and functional groups in general and iii) on the resulting functional performance. The close cooperation with funCOS 1-4 and 6 will enable us to transfer atomic scale insights obtained by surface science techniques on atomically clean, single crystalline surfaces to 2D nanostructured templates and 3D high-surface-area materials of variable structural and compositional complexity.