Nanoporous gold functionalized macrocyclic metal complexes for highly efficientphotocatalytic oxidations

在这个项目中，作为光敏剂的大环金属配合物将被固定到高表面积的金属载体，纳米多孔金（npAu）。这种新型材料组合在异质结领域提供了有前途的应用。第一个实验结果表明，金属基板上的光催化活性的增强效果，非常相反，惰性氧化物载体。树脂这可能是这种金属支撑材料的独特光学性能，并将在本研究项目中进一步研究。以下目标和工作包将是中心手段：a）制备具有不同结构尺寸（孔和韧带）的npAu衬底。这种材料提供了在约30 nm一直到微米之间精细调节孔和韧带尺寸的可能性。B）合成不同取代的大环金属配合物，金属酞菁（MPc），-亚酞菁（MsubPc），和间四苯基卟啉（MTpp）其可以以不同的吸收特性和几何形状键合到npAu衬底上，作为研究敏化剂和衬底c）将有机实体固定到npAu基底上：使用金属中心和基底之间具有不同间距的一步或两步合成程序（硫醇-连接基和-间隔基单元）。d）制备的用于光氧化反应的多相体系的催化研究：（I）测定不同体系产生单线态氧的效率（量子产率）（II）研究该体系用于不同（工业上重要的）光反应的氧化、香茅醇和苯酚的氧化的活性。

In this project macrocyclic metal complexes as photosensitizer will be immobilized onto a high surface area metallic support, the nanoporous gold (npAu). This novel materials combination offers promising applications in the field of heterogeneous photocatalysis. First experimental results indicate an enhancing effect of the metallic substrate onto the photocatalytic activitiy, very much in contrast to inert oxidic supports. Resins for this might be unique optical properties of this metallic support material and will be further investigated in this research project.The following objectives and work packages will be central means:a) Preparation of npAu substrates with different structural sizes (pores and ligaments). This material provides the possibility to finely tune the pore and ligament size between about 30 nm all the way up to microns. This enables us to balance a high porosity and areal concentration of photosensitizer and the mass transport of reactants.b) Synthesis of differently substituted macrocyclic metal-complexes, metallo phthalocyanines (MPc), -subphthalocyanines (MsubPc), and ms-tetraphenylporphyrines (MTpp) which can be bonded onto the npAu substrate with different absorption characteristics and geometries as a central means of studying the interaction between sensitizer and substrate. c) Immobilization of organic entities onto the npAu substrate: Using one- or two-step synthetic procedures (thiol-linker and -spacer units) with different spacing between the metallic centre and the substrate. d) Catalytic investigation of the prepared heterogeneous systems for photooxidation reactions: (I) determination of the efficiency for generating singlet oxygen (quantum yield) for different systems (II) investigating the activity of the system for oxidation of different (industrially important) photoreactions, the oxidation of citronellol and phenol.