Mechanism of Water Oxidation by Ferrate(VI) at pH 7-9

被引：28

作者：

Chen, Gui ^{[1
]}

Lam, William W. Y. ^{[2
,3
,4
]}

Lo, Po-Kam ^{[2
,3
]}

Man, Wai-Lun ^{[2
,3
,5
]}

Chen, Lingjing ^{[1
]}

Lau, Kai-Chung ^{[2
,3
]}

Lau, Tai-Chu ^{[2
,3
]}

机构：

[1] Dongguan Univ Technol, Sch Environm & Civil Engn, Dongguan 523808, Guangdong, Peoples R China

[2] City Univ Hong Kong, Dept Chem, Tat Chee Ave, Hong Kong, Peoples R China

[3] City Univ Hong Kong, Inst Mol Funct Mat, Tat Chee Ave, Hong Kong, Peoples R China

[4] Technol & Higher Educ Inst Hong Kong, Dept Food & Hlth Sci, Tsing Yi Rd, Hong Kong, Peoples R China

[5] Hong Kong Baptist Univ, Dept Chem, Kowloon Tong, Kowloon, Waterloo Rd, Hong Kong, Peoples R China

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2018年 / 24卷 / 70期

关键词：

DFT calculations; diferrate; ferrate; O-O coupling; water oxidation; EFFECTIVE CORE POTENTIALS; O BOND FORMATION; SINGLE-SITE; AB-INITIO; RUTHENIUM(II) COMPLEXES; MOLECULAR CALCULATIONS; OXYGEN EVOLUTION; DIMER COMPLEX; CATALYST; KINETICS;

D O I：

10.1002/chem.201803757

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The kinetics of water oxidation by K2FeO4 has been reinvestigated by UV/Vis spectrophotometry from pH 7-9 in 0.2 m phosphate buffer. The rate of reaction was found to be second-order in both [FeO42-] and [H+]. These results are consistent with a proposed mechanism in which the first step involves the initial equilibrium protonation of FeO42- to give FeO3(OH)(-), which then undergoes rate-limiting O-O bond formation. Analysis of the O-2 isotopic composition for the reaction in (H2O)-O-18 suggests that the predominant pathway for water oxidation by ferrate is intramolecular O-O coupling. DFT calculations have also been performed, which support the proposed mechanism.

引用

页码：18735 / 18742

页数：8

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