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New multinuclear metal catalysts for the light-driven activation of water and reduction of CO2

用于光驱动水活化和二氧化碳还原的新型多核金属催化剂

基本信息

批准号：
177906372
负责人：
Dr. Matthias Schwalbe
金额：
--
依托单位：
Department of Chemistry
依托单位国家：
德国
项目类别：
Research Grants
财政年份：
2010
资助国家：
德国
起止时间：
2009-12-31 至 2016-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/177906372?language=en
关键词：
New multinuclear metal catalysts light

项目摘要

First hetero-oligonuclear metal-organic compounds for the activation of water and carbon monoxide have been prepared. Their (photo)catalytic properties are currently investigated and reaction conditions are optimized. With the experiences gained new optimized catalysts for the production of hydrogen and oxygen (hydrogen fuel cell fuels) as well as CO or HCOOH as C1 building blocks shall be synthesized. In those systems, the connection of a photoactive unit with a catalytic active unit plays a major role. A well-directed photo-electron-transfer (PET) enables the provision of the required electron equivalents or holes in these photo-catalysts.The oxidation of oxid-ions to O2 and its backreaction (O2 to H2O or H2O2), respectively, are to be investigated especially with compounds of the Hangman- and Pacman-type. The specific introduction of substituents and catalytic metal center will determine the direction of the reaction. On the one hand, ruthenium polypyridyl compounds and on the other hand high-valent manganese and iron porphyrinoids shall be employed as catalytic active unit. Studies on reduction processes, especially the light-activated reduction of CO2, are to happen using supramolecular compounds. Extended porphyrinic macrocycles function as a bridging ligand and are arranged in a way to connect a photoactive center capturing light energy with a catalytic active metal center.The investigation of the controllability of the planned organic transformations by light, pH value, substituents and other parameters is supposed to lead to a precise product selectivity. Additionally, new insights into the elapsing processes and mechanisms shall be provided by isolation and characterization of reactive intermediates.

首先制备了用于活化水和一氧化碳的杂寡金属有机化合物。目前，他们的（光）催化性能进行了研究，并优化了反应条件。利用所获得的经验，将合成用于生产氢气和氧气（氢燃料电池燃料）以及作为C1结构单元的CO或HCOOH的新的优化催化剂。在这些系统中，光活性单元与催化活性单元的连接起主要作用。良好的定向光电子转移（PET）使得能够在这些光催化剂中提供所需的电子当量或空穴。氧化物离子氧化成O2及其逆反应（O2到H2O或H2O2）分别将被研究，特别是Hangman型和Pacman型化合物。取代基和催化金属中心的具体引入将决定反应的方向。一方面，钌多吡啶化合物和另一方面，高价锰和铁卟啉类化合物将被用作催化活性单元。还原过程的研究，特别是CO2的光活化还原，将使用超分子化合物进行。扩展卟啉大环作为桥连配体，将捕获光能的光活性中心与催化活性金属中心连接起来，研究光、pH值、取代基等参数对有机转化的可控性，可以得到精确的产物选择性.此外，通过分离和表征活性中间体，将提供对流逝过程和机制的新见解。