Multinuclear Metal Complex Photosensitizers Covalently-Coupled to Cobalt-based Catalysts for Hydrogen Evolution

多核金属配合物光敏剂与钴基催化剂共价偶联用于析氢

• 批准号: 399786739
• 负责人: Dr. Kevin Barthelmes
• 金额: --
• 依托单位: Department of Materials and Applied Chemistry
• 依托单位国家: 德国
• 项目类别: Research Fellowships
• 财政年份: 2018
• 资助国家: 德国
• 起止时间: 2017-12-31 至 2020-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/399786739?language=en
• 关键词: Multinuclear; Metal; Complex; Photosensitizers; Covalently

In the last decades, tremendous research has been focused on the conversion of solar energy into chemical energy. In this regard, photocatalytic processes play a crucial role to produce so-called “solar fuels”. Oxygen and hydrogen are two important solar fuels and can be generated by the catalytic oxidation of water and reduction of protons, respectively. The two main components of a photocatalytic device are the photosensitizer and the catalyst. Recent developments could significantly improve the performance of both components. For example, multinuclear ruthenium(II) polypyridyl complexes as photosensitizer have been employed for the photocatalytic oxygen evolution reaction to increase the sunlight absorption and they are capable to absorb lower-energetic solar light. However, multinuclear complexes are rarely described in literature for the similar hydrogen evolution reaction, usually mononuclear complexes are used. On the other hand, a new family of molecular cobalt(II) polypyridyl complexes as catalysts for hydrogen evolution has recently emerged. These catalysts proved to be more robust than other systems and display higher activities for electrocatalysis in pure water. For this reason, the research plan is a combination of these two recent developments in photocatalytic systems. To further increase efficiency of the designed systems, another aim is the covalent linkage of photosensitizer and catalyst. By this approach, the excess of photosensitizer to catalyst can be avoided and the electron-transfer process from the photosensitizer to the catalyst will be facilitated. The designed systems should possess distinctly higher photocatalytic activity in aqueous solutions than previously reported systems. Moreover, it is expected to afford an efficient photocatalytic system, which utilize a wide range of the visible to near-infrared solar spectrum. This could be a major impact for the development of new systems, because photocatalysis in aqueous solutions with low-energetic light is still challenging.

在过去的几十年里，大量的研究集中在太阳能转化为化学能。在这方面，光催化过程在生产所谓的“太阳能燃料”方面发挥着至关重要的作用。氧气和氢气是两种重要的太阳能燃料，可以分别通过水的催化氧化和质子的还原来产生。光催化装置的两个主要组成部分是光敏剂和催化剂。最近的事态发展可以大大改善这两个组成部分的性能。例如，多核钌（II）多吡啶络合物作为光敏剂已用于光催化析氧反应以增加太阳光吸收，并且它们能够吸收较低能量的太阳光。然而，多核配合物很少在文献中描述类似的析氢反应，通常使用单核配合物。另一方面，最近出现了一个新的分子钴（II）多吡啶配合物作为析氢催化剂的家庭。这些催化剂被证明是更强大的比其他系统，并显示出较高的活性，在纯水中的电催化。出于这个原因，研究计划是光催化系统中这两个最新发展的结合。为了进一步提高所设计的系统的效率，另一个目的是光敏剂和催化剂的共价连接。通过这种方法，可以避免光敏剂对催化剂的过量，并且将促进从光敏剂到催化剂的电子转移过程。所设计的系统应具有明显更高的光催化活性在水溶液中比以前报道的系统。此外，预期提供有效的光催化系统，其利用宽范围的可见光到近红外太阳光谱。这可能会对新系统的开发产生重大影响，因为用低能光在水溶液中发光仍然具有挑战性。