A noble-metal-free system for photocatalytic hydrogen production from water.
A noble-metal-free system for photocatalytic hydrogen production from water.
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DOI：
10.1002/chem.201302091
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发表时间：
2013-11
期刊：
影响因子：
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通讯作者：
E. Mejía;Shu‐Ping Luo;M. Karnahl;Aleksej Friedrich;S. Tschierlei;Annette‐Enrica Surkus;H. Junge;
中科院分区：
文献类型：
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作者：
E. Mejía;Shu‐Ping Luo;M. Karnahl;Aleksej Friedrich;S. Tschierlei;Annette‐Enrica Surkus;H. Junge;
通过使用[Fe3(CO)12]作为水还原催化剂(WRC)，制备了一系列具有双齿PP和NN螯合配体的杂配铜(I)配合物，并成功应用于光驱动制氢中的光敏剂。这些系统有效地减少水/THF/三乙胺混合物中的质子，其中胺充当牺牲电子供体（SR）。使用这些完全不含贵金属的系统获得了高达 1330 的周转数（对于 H）。对新配合物进行了电化学和光物理表征。他们展示了 MLCT 激发态的寿命与其作为质子还原系统中光敏剂的效率之间的相关性。在这些实验中，观察到了长达 54 μs 的相当长的激发态寿命。在存在和不存在 WRC 的情况下，用 SR 进行的猝灭研究表明，在前一种情况下，分子内失活效率更高，从而表明氧化猝灭途径占主导地位。
A series of heteroleptic copper(I) complexes with bidentate PP and NN chelate ligands was prepared and successfully applied as photosensitizers in the light-driven production of hydrogen, by using [Fe3(CO)12] as a water-reduction catalyst (WRC). These systems efficiently reduces protons from water/THF/triethylamine mixtures, in which the amine serves as a sacrificial electron donor (SR). Turnover numbers (for H) up to 1330 were obtained with these fully noble-metal-free systems. The new complexes were electrochemically and photophysically characterized. They exhibited a correlation between the lifetimes of the MLCT excited state and their efficiency as photosensitizers in proton-reduction systems. Within these experiments, considerably long excited-state lifetimes of up to 54 μs were observed. Quenching studies with the SR, in the presence and absence of the WRC, showed that intramolecular deactivation was more efficient in the former case, thus suggesting the predominance of an oxidative quenching pathway.