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Identifying MnVII-oxo Species during Electrochemical Water Oxidation by Manganese Oxide.


ABSTRACT: Identifying surface active intermediate species is essential to reveal the catalytic mechanism of water oxidation by metal-oxides-based catalysts and to develop more efficient catalysts for oxygen-oxygen bond formation. Here we report, through electrochemical methods and ex situ infrared spectroscopy, the identification of a MnVII = O intermediate during catalytic water oxidation by a c-disordered ?-MnOx with an onset-potential-dependent reduction peak at 0.93 V and an infrared peak at 912 cm-1. This intermediate is proved to be highly reactive and much more oxidative than permanganate ion. Therefore, we propose a new catalytic mechanism for water oxidation catalyzed by Mn oxides, with involvement of the MnVII = O intermediate in a resting state and the MnIV-O-MnVII = O as a real active species for oxygen-oxygen bond formation.

SUBMITTER: Zhang B 

PROVIDER: S-EPMC6147022 | biostudies-literature | 2018 Jun

REPOSITORIES: biostudies-literature

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Identifying Mn<sup>VII</sup>-oxo Species during Electrochemical Water Oxidation by Manganese Oxide.

Zhang Biaobiao B   Daniel Quentin Q   Fan Lizhou L   Liu Tianqi T   Meng Qijun Q   Sun Licheng L  

iScience 20180530


Identifying surface active intermediate species is essential to reveal the catalytic mechanism of water oxidation by metal-oxides-based catalysts and to develop more efficient catalysts for oxygen-oxygen bond formation. Here we report, through electrochemical methods and ex situ infrared spectroscopy, the identification of a Mn<sup>VII</sup> = O intermediate during catalytic water oxidation by a c-disordered δ-MnO<sub>x</sub> with an onset-potential-dependent reduction peak at 0.93 V and an infr  ...[more]

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