Iron-iron hydrogenase active subunit covalently linking to organic chromophore for light-driven hydrogen evolution
Iron-iron hydrogenase active subunit covalently linking to organic chromophore for light-driven hydrogen evolution
复制标题
铁-铁氢化酶活性亚基与有机发色团共价连接，用于光驱动析氢
DOI：
10.1016/j.ijhydene.2014.05.003
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发表时间：
2014-07-03
影响因子：
7.2
通讯作者：
Zhao, Jianxun
中科院分区：
文献类型：
--
作者：
Gao, Shang;Huang, Shuai;Zhao, Jianxun
以苯并噻唑为光敏剂，通过一种简单易行的方法成功构建了第一个光催化[FeFe]-氢化酶（[FeFe]-H（2）ase）模拟物3，并通过各种光谱和X射线晶体学技术对其进行了表征。稳态光谱和电化学测试结果表明，在3. 5 ~ 4. 5 mol/L的溶液中发生了光诱导电子转移。通过激光闪光光解进一步证实了还原的[（FeFe 0）-Fe-1]物种，并认为其是光驱动H-2演化的原因。结果，在质子源存在下由光催化剂3和牺牲电子供体组成的光催化体系在光照射下确实产生了转化数（TON）为24.2的H-2。光催化活性测试表明，光敏剂与催化中心共价结合形成的[FeFe]-H（2）酶模拟物具有显著的光催化活性。结果表明，该合成策略在构建紧凑、廉价、易得的[FeFe]-H（2）ase模型配合物作为光催化剂方面具有巨大的潜力。版权所有（C）2014，氢能出版物有限责任公司。由爱思唯尔有限公司出版。保留所有权利。
The first photocatalytic [FeFe]-hydrogenase ([FeFe]-H(2)ase) mimic 3 with noble-metal-free benzothiazole as donating photosensitizer had been successfully constructed via an easily accessible approach, and fully characterized by various spectroscopic and X-ray crystallographic techniques. Steady-state spectroscopy and electrochemistry revealed the evidences indicating that the photo-induced electron transfer occurred in 3. The reduced [(FeFe0)-Fe-1] species was further confirmed by laser flash photolysis and considered to be responsible for the light-driven H-2 evolution. As a result, the photocatalytic system consisting of the photocatalyst 3 and the sacrificial electron donor in the presence of proton source indeed produced H-2 with a turnover number (TON) of 24.2 under light irradiation. The TON indicated a remarkably photocatalytic efficiency for an [FeFe]-H(2)ase mimic assembled by the covalent combination of a photosensitizer to the catalytic center. The results demonstrated the tremendous potential of present synthetic strategy for the construction of compact, inexpensive, easily accessible [FeFe]-H(2)ase model complexes as photocatalysts. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.