Electrocatalytic investigations of a tri-iron cluster towards hydrogen evolution and relevance to [FeFe]-hydrogenase

被引：35

作者：

Li, Zhimei ^{[1
]}

Zeng, Xianghua ^{[1
]}

Niu, Zhigang ^{[1
]}

Liu, Xiaoming ^{[1
]}

机构：

[1] Nanchang Univ, Dept Chem, Inst Adv Study, Nanchang 330031, Jiangxi, Peoples R China

来源：

ELECTROCHIMICA ACTA | 2009年 / 54卷 / 13期

关键词：

FeFe]-hydrogenase; Iron-sulfur-carbonyl cluster; Electrocatalytic hydrogen evolution; Electrochemical mechanism; FE-ONLY HYDROGENASE; ACTIVE-SITE; ELECTRON-TRANSFER; CRYSTAL-STRUCTURE; TRIIRON CLUSTERS; LIGAND SUBSTITUTION; PROTON REDUCTION; DIIRON SUBSITE; WEAK ACIDS; COMPLEXES;

D O I：

10.1016/j.electacta.2009.01.034

中图分类号：

O646 [电化学、电解、磁化学];

学科分类号：

081704 ;

摘要：

Electrochemical investigations of a tri-iron cluster, [Fe-3(mu(3)-S)(2)(CO)(9)] (designated as Fe3CO thereafter), which possesses a core of [(FeFeFeI)-Fe-II-Fe-I], is described. In 0.5 M [NBu4]BF4/dichloromethane, the cluster exhibits a fairly reversible redox process at -1.03 V and irreversible reduction wave at ca. -1.75 V. The latter is attributed to the reductions of both the decomposed product of the monoanion, [Fe3CO](center dot-), and the isomer of this anion. This cluster catalyses proton reduction with the presence of acid HBF4-Et2O in dichloromethane. Possible mechanisms were proposed to elucidate its electrochemistry and electrocatalytic behaviours on proton reduction. Digital simulations were performed to verify the proposed mechanisms and kinetic parameters were generated at our best estimation in the simulations. The simulated cyclic voltammograms fit well with the experimentally observed ones, which largely supports the proposed mechanisms. (C) 2009 Elsevier Ltd. All rights reserved.

引用

页码：3638 / 3644

页数：7

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