Cargando…

Identifying Mn(VII)-oxo Species during Electrochemical Water Oxidation by Manganese Oxide

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 spectroscop...

Descripción completa

Detalles Bibliográficos
Autores principales: Zhang, Biaobiao, Daniel, Quentin, Fan, Lizhou, Liu, Tianqi, Meng, Qijun, Sun, Licheng
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Elsevier 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6147022/
https://www.ncbi.nlm.nih.gov/pubmed/30240736
http://dx.doi.org/10.1016/j.isci.2018.05.018
_version_ 1783356497600708608
author Zhang, Biaobiao
Daniel, Quentin
Fan, Lizhou
Liu, Tianqi
Meng, Qijun
Sun, Licheng
author_facet Zhang, Biaobiao
Daniel, Quentin
Fan, Lizhou
Liu, Tianqi
Meng, Qijun
Sun, Licheng
author_sort Zhang, Biaobiao
collection PubMed
description 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(VII) = O intermediate during catalytic water oxidation by a c-disordered δ-MnO(x) 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 Mn(VII) = O intermediate in a resting state and the Mn(IV)−O−Mn(VII) = O as a real active species for oxygen-oxygen bond formation.
format Online
Article
Text
id pubmed-6147022
institution National Center for Biotechnology Information
language English
publishDate 2018
publisher Elsevier
record_format MEDLINE/PubMed
spelling pubmed-61470222018-10-02 Identifying Mn(VII)-oxo Species during Electrochemical Water Oxidation by Manganese Oxide Zhang, Biaobiao Daniel, Quentin Fan, Lizhou Liu, Tianqi Meng, Qijun Sun, Licheng iScience Article 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(VII) = O intermediate during catalytic water oxidation by a c-disordered δ-MnO(x) 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 Mn(VII) = O intermediate in a resting state and the Mn(IV)−O−Mn(VII) = O as a real active species for oxygen-oxygen bond formation. Elsevier 2018-05-30 /pmc/articles/PMC6147022/ /pubmed/30240736 http://dx.doi.org/10.1016/j.isci.2018.05.018 Text en © 2018 The Authors http://creativecommons.org/licenses/by/4.0/ This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Zhang, Biaobiao
Daniel, Quentin
Fan, Lizhou
Liu, Tianqi
Meng, Qijun
Sun, Licheng
Identifying Mn(VII)-oxo Species during Electrochemical Water Oxidation by Manganese Oxide
title Identifying Mn(VII)-oxo Species during Electrochemical Water Oxidation by Manganese Oxide
title_full Identifying Mn(VII)-oxo Species during Electrochemical Water Oxidation by Manganese Oxide
title_fullStr Identifying Mn(VII)-oxo Species during Electrochemical Water Oxidation by Manganese Oxide
title_full_unstemmed Identifying Mn(VII)-oxo Species during Electrochemical Water Oxidation by Manganese Oxide
title_short Identifying Mn(VII)-oxo Species during Electrochemical Water Oxidation by Manganese Oxide
title_sort identifying mn(vii)-oxo species during electrochemical water oxidation by manganese oxide
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6147022/
https://www.ncbi.nlm.nih.gov/pubmed/30240736
http://dx.doi.org/10.1016/j.isci.2018.05.018
work_keys_str_mv AT zhangbiaobiao identifyingmnviioxospeciesduringelectrochemicalwateroxidationbymanganeseoxide
AT danielquentin identifyingmnviioxospeciesduringelectrochemicalwateroxidationbymanganeseoxide
AT fanlizhou identifyingmnviioxospeciesduringelectrochemicalwateroxidationbymanganeseoxide
AT liutianqi identifyingmnviioxospeciesduringelectrochemicalwateroxidationbymanganeseoxide
AT mengqijun identifyingmnviioxospeciesduringelectrochemicalwateroxidationbymanganeseoxide
AT sunlicheng identifyingmnviioxospeciesduringelectrochemicalwateroxidationbymanganeseoxide