Nanoporous gold functionalized macrocyclic metal complexes for highly efficientphotocatalytic oxidations

在这个项目中，大环金属配合物作为光敏剂将被固定在一个高表面积的金属载体，纳米孔金（npAu）。这种新型材料组合在非均相光催化领域具有广阔的应用前景。首先，实验结果表明金属衬底对光催化活性有增强作用，这与惰性氧化载体有很大的不同。这种树脂可能是这种金属支撑材料独特的光学特性，将在本研究项目中进一步研究。以下目标和工作包将是主要手段：a)制备具有不同结构尺寸（孔隙和韧带）的npAu底物。这种材料提供了在30纳米到微米之间微调孔和韧带大小的可能性。这使我们能够平衡高孔隙率和光敏剂的面积浓度以及反应物的质量传输。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ms-四苯基卟啉（MTpp），它们可以结合在具有不同吸收特性和几何形状的npAu底物上，作为研究敏化剂与底物相互作用的主要手段。c)将有机实体固定在npAu衬底上：使用一步或两步合成程序（硫醇连接单元和间隔单元），金属中心与衬底之间的间距不同。d)制备的非均相光氧化反应体系的催化研究：(I)测定不同体系生成单线态氧的效率（量子产率）（II）研究该体系氧化不同（工业上重要的）光反应的活性，如香茅醛和苯酚的氧化。

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.