Electrocatalytic water oxidation with manganese phosphates
Abstract As inspired by the Mn4CaO5 oxygen evolution center in nature, Mn-based electrocatalysts have received overwhelming attention for water oxidation. However, the understanding of the detailed reaction mechanism has been a long-standing problem. Herein, homologous KMnPO4 and KMnPO4•H2O with 4-c...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2024-02-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-45705-1 |
| _version_ | 1797274054349029376 |
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| author | Shujiao Yang Kaihang Yue Xiaohan Liu Sisi Li Haoquan Zheng Ya Yan Rui Cao Wei Zhang |
| author_facet | Shujiao Yang Kaihang Yue Xiaohan Liu Sisi Li Haoquan Zheng Ya Yan Rui Cao Wei Zhang |
| author_sort | Shujiao Yang |
| collection | DOAJ |
| description | Abstract As inspired by the Mn4CaO5 oxygen evolution center in nature, Mn-based electrocatalysts have received overwhelming attention for water oxidation. However, the understanding of the detailed reaction mechanism has been a long-standing problem. Herein, homologous KMnPO4 and KMnPO4•H2O with 4-coordinated and 6-coordinated Mn centers, respectively, are prepared. The two catalysts constitute an ideal platform to study the structure-performance correlation. The presence of Mn(III), Mn(IV), and Mn(V) intermediate species are identified during water oxidation. The Mn(V)=O species is demonstrated to be the substance for O−O bond formation. In KMnPO4•H2O, the Mn coordination structure did not change significantly during water oxidation. In KMnPO4, the Mn coordination structure changed from 4-coordinated [MnO4] to 5-coordinated [MnO5] motif, which displays a triangular biconical configuration. The structure flexibility of [MnO5] is thermodynamically favored in retaining Mn(III)−OH and generating Mn(V)=O. The Mn(V)=O species is at equilibrium with Mn(IV)=O, the concentration of which determines the intrinsic activity of water oxidation. This study provides a clear picture of water oxidation mechanism on Mn-based systems. |
| first_indexed | 2024-03-07T14:52:53Z |
| format | Article |
| id | doaj.art-c3cddb43f0b347b18f784aa3647210d3 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-07T14:52:53Z |
| publishDate | 2024-02-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-c3cddb43f0b347b18f784aa3647210d32024-03-05T19:37:56ZengNature PortfolioNature Communications2041-17232024-02-0115111310.1038/s41467-024-45705-1Electrocatalytic water oxidation with manganese phosphatesShujiao Yang0Kaihang Yue1Xiaohan Liu2Sisi Li3Haoquan Zheng4Ya Yan5Rui Cao6Wei Zhang7Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education; School of Chemistry and Chemical Engineering, Shaanxi Normal UniversityShanghai Institute of Ceramics, Chinese Academy of Sciences (SICCAS)Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education; School of Chemistry and Chemical Engineering, Shaanxi Normal UniversityKey Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education; School of Chemistry and Chemical Engineering, Shaanxi Normal UniversityKey Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education; School of Chemistry and Chemical Engineering, Shaanxi Normal UniversityShanghai Institute of Ceramics, Chinese Academy of Sciences (SICCAS)Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education; School of Chemistry and Chemical Engineering, Shaanxi Normal UniversityKey Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education; School of Chemistry and Chemical Engineering, Shaanxi Normal UniversityAbstract As inspired by the Mn4CaO5 oxygen evolution center in nature, Mn-based electrocatalysts have received overwhelming attention for water oxidation. However, the understanding of the detailed reaction mechanism has been a long-standing problem. Herein, homologous KMnPO4 and KMnPO4•H2O with 4-coordinated and 6-coordinated Mn centers, respectively, are prepared. The two catalysts constitute an ideal platform to study the structure-performance correlation. The presence of Mn(III), Mn(IV), and Mn(V) intermediate species are identified during water oxidation. The Mn(V)=O species is demonstrated to be the substance for O−O bond formation. In KMnPO4•H2O, the Mn coordination structure did not change significantly during water oxidation. In KMnPO4, the Mn coordination structure changed from 4-coordinated [MnO4] to 5-coordinated [MnO5] motif, which displays a triangular biconical configuration. The structure flexibility of [MnO5] is thermodynamically favored in retaining Mn(III)−OH and generating Mn(V)=O. The Mn(V)=O species is at equilibrium with Mn(IV)=O, the concentration of which determines the intrinsic activity of water oxidation. This study provides a clear picture of water oxidation mechanism on Mn-based systems.https://doi.org/10.1038/s41467-024-45705-1 |
| spellingShingle | Shujiao Yang Kaihang Yue Xiaohan Liu Sisi Li Haoquan Zheng Ya Yan Rui Cao Wei Zhang Electrocatalytic water oxidation with manganese phosphates Nature Communications |
| title | Electrocatalytic water oxidation with manganese phosphates |
| title_full | Electrocatalytic water oxidation with manganese phosphates |
| title_fullStr | Electrocatalytic water oxidation with manganese phosphates |
| title_full_unstemmed | Electrocatalytic water oxidation with manganese phosphates |
| title_short | Electrocatalytic water oxidation with manganese phosphates |
| title_sort | electrocatalytic water oxidation with manganese phosphates |
| url | https://doi.org/10.1038/s41467-024-45705-1 |
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