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一种新型双核钌配合物作为高效水氧化催化剂。

A new dinuclear ruthenium complex as an efficient water oxidation catalyst.

作者信息

Xu Yunhua, Akermark Torbjörn, Gyollai Viktor, Zou Dapeng, Eriksson Lars, Duan Lele, Zhang Rong, Akermark Björn, Sun Licheng

机构信息

Organic Chemistry, School of Chemical Science and Engineering, Royal Institute of Technology (KTH), 100 44 Stockholm, Sweden.

出版信息

Inorg Chem. 2009 Apr 6;48(7):2717-9. doi: 10.1021/ic802052u.

Abstract

A dinuclear ruthenium complex, which acts as a molecular catalyst for water oxidation, has been synthesized and characterized. The electronic and electrochemical properties were studied by UV-vis spectroscopy and cyclic voltammetry. The oxidation potentials of the complex are significantly lowered by introducing a negatively charged carboxylate ligand, in comparison with those of the reported complexes that have neutral ligands. The catalytic activity of the complex toward water oxidation using Ce(NH(4))(2)(NO(3))(6) as a chemical oxidant was investigated by means of an oxygen electrode and mass spectrometry. The turnover number of this catalyst with Ce(IV) as the chemical oxidant was found to be ca. 1700. The mass spectroscopic analysis of the isotopomer distribution in oxygen evolved from (18)O-labeled water indicates that O atoms in the evolved oxygen originate from water.

摘要

一种作为水氧化分子催化剂的双核钌配合物已被合成并表征。通过紫外可见光谱和循环伏安法研究了其电子和电化学性质。与具有中性配体的已报道配合物相比,通过引入带负电荷的羧酸盐配体,该配合物的氧化电位显著降低。使用铈(IV)铵硝酸盐[Ce(NH₄)₂(NO₃)₆]作为化学氧化剂,通过氧电极和质谱法研究了该配合物对水氧化的催化活性。发现以Ce(IV)作为化学氧化剂时,该催化剂的周转数约为1700。对由¹⁸O标记水产生的氧气中同位素异构体分布的质谱分析表明,产生的氧气中的O原子来自水。

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