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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...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Elsevier
2018
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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 |
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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 |
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