Electrocatalytic investigations of a tri-iron cluster towards hydrogen evolution and relevance to [FeFe]-hydrogenase
Electrocatalytic investigations of a tri-iron cluster towards hydrogen evolution and relevance to [FeFe]-hydrogenase
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DOI：
10.1016/j.electacta.2009.01.034
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发表时间：
2009-05
影响因子：
6.6
通讯作者：
Zhimei Li;Xianghua Zeng;Zhigang Niu;Xiaoming Liu
中科院分区：
文献类型：
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作者：
Zhimei Li;Xianghua Zeng;Zhigang Niu;Xiaoming Liu
本文报道了以[FeIIFeIFeI]为核的三价铁原子簇[Fe_3（μ ~ 3-S）_2（CO）_9]（以下简称Fe_3CO）的电化学研究。在0.5M [NBu 4] BF 4/二氯甲烷溶液中，该簇合物在-1.03V处有一个可逆的氧化还原过程，在约100 V处有一个不可逆的还原波。-1.75V。后者归因于单阴离子的分解产物[Fe 3CO]−和该阴离子的异构体的还原。该簇合物在酸HBF 4·Et 2 O存在下催化质子还原。提出了可能的机理，以阐明其电化学和电催化质子还原的行为。进行了数字模拟，以验证所提出的机制和动力学参数产生在我们最好的估计在模拟。模拟的循环伏安图与实验观察到的吻合良好，这在很大程度上支持了所提出的机制。
Electrochemical investigations of a tri-iron cluster, [Fe3(μ3-S)2(CO)9] (designated as Fe3CO thereafter), which possesses a core of [FeIIFeIFeI], is described. In 0.5M [NBu4]BF4/dichloromethane, the cluster exhibits a fairly reversible redox process at −1.03V and irreversible reduction wave at ca. −1.75V. The latter is attributed to the reductions of both the decomposed product of the monoanion, [Fe3CO]−, 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.