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Nanoporous gold functionalized macrocyclic metal complexes for highly efficientphotocatalytic oxidations

用于高效光催化氧化的纳米孔金功能化大环金属配合物

基本信息

批准号：
290346172
负责人：
Dr. Arne Wittstock
金额：
--
依托单位：
Institut für Organische und Analytische Chemie
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2016
资助国家：
德国
起止时间：
2015-12-31 至 2019-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/290346172?language=en
关键词：
Nanoporous gold functionalized macrocyclic metal

项目摘要

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.

在该项目中，作为光敏剂的大环金属配合物将被固定在高表面积金属载体——纳米多孔金（npAu）上。这种新颖的材料组合在异质光催化领域提供了有前景的应用。第一个实验结果表明金属基材对光催化活性的增强作用，与惰性氧化物载体形成鲜明对比。用于此目的的树脂可能是这种金属支撑材料的独特光学特性，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 基底。这种材料提供了在约 30 nm 一直到微米之间微调孔和韧带尺寸的可能性。这使我们能够平衡光敏剂的高孔隙率和面积浓度以及反应物的传质。 b) 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) 的合成，它们可以用不同的方式键合到 npAu 基底上。吸收特性和几何形状作为研究敏化剂和底物之间相互作用的中心手段。 c) 将有机实体固定到 npAu 基底上：使用一步或两步合成程序（硫醇连接基和间隔单元），金属中心和基底之间的间距不同。 d) 制备的用于光氧化反应的多相系统的催化研究：(I) 测定不同系统产生单线态氧的效率（量子产率）（II) 研究系统对不同（工业上重要的）光反应的氧化活性，即香茅醇和苯酚的氧化。