Self-assembled biomimetic [2Fe2S]-hydrogenase-based photocatalyst for molecular hydrogen evolution
Self-assembled biomimetic [2Fe2S]-hydrogenase-based photocatalyst for molecular hydrogen evolution
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DOI：
10.1073/pnas.0809666106
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发表时间：
2009-06-30
影响因子：
11.1
通讯作者：
Reek, J. N. H.
中科院分区：
文献类型：
--
作者：
Kluwer, A. M.;Kapre, R.;Reek, J. N. H.
清洁能源的大规模生产是当今社会面临的主要挑战之一。分子氢被设想为未来的一种关键绿色燃料，但它只有在以清洁的方式生产时才能成为传统燃料的可持续替代品。在这里，我们报告了一种超分子仿生方法，形成一种催化剂，利用光作为能源产生分子氢。它由发色团组装到基于氢化酶催化剂的双（硫醇盐）桥接的二铁（[2Fe 2S]）上组成。本文中介绍的超分子构建块方法使得能够容易地形成一系列复合物，这些复合物都被彻底表征，揭示了催化剂组装体的光活性强烈依赖于其性质。由不同的配合物形成的活性物种似乎是[Fe-2（mu-pdt）（CO）（4）{PPh 2（4-py）}（2）]（3）与两种不同类型的卟啉（5a和5 b）配位。
The large-scale production of clean energy is one of the major challenges society is currently facing. Molecular hydrogen is envisaged as a key green fuel for the future, but it becomes a sustainable alternative for classical fuels only if it is also produced in a clean fashion. Here, we report a supramolecular biomimetic approach to form a catalyst that produces molecular hydrogen using light as the energy source. It is composed of an assembly of chromophores to a bis(thiolate)-bridged diiron ([2Fe2S]) based hydrogenase catalyst. The supramolecular building block approach introduced in this article enabled the easy formation of a series of complexes, which are all thoroughly characterized, revealing that the photoactivity of the catalyst assembly strongly depends on its nature. The active species, formed from different complexes, appears to be the [Fe-2(mu-pdt)(CO)(4){PPh2(4-py)}(2)] (3) with 2 different types of porphyrins (5a and 5b) coordinated to it. The modular supramolecular approach was important in this study as with a limited number of building blocks several different complexes were generated.