Operando monitoring of the functional role of tetrahedral cobalt centers for the oxygen evolution reaction
Abstract The complexity of the intrinsic oxygen evolution reaction (OER) mechanism, particularly the precise relationships between the local coordination geometry of active metal centers and the resulting OER kinetics, remains to be fully understood. Herein, we construct a series of 3 d transition m...
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Nature Portfolio
2025-01-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-55857-3 |
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| author | Yonggui Zhao Nanchen Dongfang Chong Huang Rolf Erni Jingguo Li Han Zhao Long Pan Marcella Iannuzzi Greta R. Patzke |
| author_facet | Yonggui Zhao Nanchen Dongfang Chong Huang Rolf Erni Jingguo Li Han Zhao Long Pan Marcella Iannuzzi Greta R. Patzke |
| author_sort | Yonggui Zhao |
| collection | DOAJ |
| description | Abstract The complexity of the intrinsic oxygen evolution reaction (OER) mechanism, particularly the precise relationships between the local coordination geometry of active metal centers and the resulting OER kinetics, remains to be fully understood. Herein, we construct a series of 3 d transition metal-incorporated cobalt hydroxide-based nanobox architectures for the OER which contain tetrahedrally coordinated Co(II) centers. Combination of bulk- and surface-sensitive operando spectroelectrochemical approaches reveals that tetrahedral Co(II) centers undergo a dynamic transformation into highly active Co(IV) intermediates acting as the true OER active species which activate lattice oxygen during the OER. Such a dynamic change in the local coordination geometry of Co centers can be further facilitated by partial Fe incorporation. In comparison, the formation of such active Co(IV) species is found to be hindered in CoOOH and Co-FeOOH, which are predominantly containing [CoIIIO6] and [CoII/FeIIIO6] octahedra, respectively, but no mono-μ-oxo-bridged [CoIIO4] moieties. This study offers a comprehensive view of the dynamic role of local coordination geometry of active metal centers in the OER kinetics. |
| format | Article |
| id | doaj-art-0bf543cac42245889fbd985068134858 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Nature Portfolio |
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| series | Nature Communications |
| spelling | doaj-art-0bf543cac42245889fbd9850681348582025-01-12T12:31:40ZengNature PortfolioNature Communications2041-17232025-01-0116111510.1038/s41467-025-55857-3Operando monitoring of the functional role of tetrahedral cobalt centers for the oxygen evolution reactionYonggui Zhao0Nanchen Dongfang1Chong Huang2Rolf Erni3Jingguo Li4Han Zhao5Long Pan6Marcella Iannuzzi7Greta R. Patzke8Department of Chemistry, University of ZurichDepartment of Chemistry, University of ZurichDepartment of Chemistry, University of ZurichElectron Electron Microscopy Center, Empa, Swiss Federal Laboratories for Materials Science and TechnologyDepartment of Environmental Science and Engineering, CAS Key Laboratory of Urban Pollutant Conversion, University of Science and Technology of ChinaDepartment of Chemistry, University of ZurichKey Laboratory of Advanced Metallic Materials of Jiangsu Province, School of Materials Science and Engineering, Southeast UniversityDepartment of Chemistry, University of ZurichDepartment of Chemistry, University of ZurichAbstract The complexity of the intrinsic oxygen evolution reaction (OER) mechanism, particularly the precise relationships between the local coordination geometry of active metal centers and the resulting OER kinetics, remains to be fully understood. Herein, we construct a series of 3 d transition metal-incorporated cobalt hydroxide-based nanobox architectures for the OER which contain tetrahedrally coordinated Co(II) centers. Combination of bulk- and surface-sensitive operando spectroelectrochemical approaches reveals that tetrahedral Co(II) centers undergo a dynamic transformation into highly active Co(IV) intermediates acting as the true OER active species which activate lattice oxygen during the OER. Such a dynamic change in the local coordination geometry of Co centers can be further facilitated by partial Fe incorporation. In comparison, the formation of such active Co(IV) species is found to be hindered in CoOOH and Co-FeOOH, which are predominantly containing [CoIIIO6] and [CoII/FeIIIO6] octahedra, respectively, but no mono-μ-oxo-bridged [CoIIO4] moieties. This study offers a comprehensive view of the dynamic role of local coordination geometry of active metal centers in the OER kinetics.https://doi.org/10.1038/s41467-025-55857-3 |
| spellingShingle | Yonggui Zhao Nanchen Dongfang Chong Huang Rolf Erni Jingguo Li Han Zhao Long Pan Marcella Iannuzzi Greta R. Patzke Operando monitoring of the functional role of tetrahedral cobalt centers for the oxygen evolution reaction Nature Communications |
| title | Operando monitoring of the functional role of tetrahedral cobalt centers for the oxygen evolution reaction |
| title_full | Operando monitoring of the functional role of tetrahedral cobalt centers for the oxygen evolution reaction |
| title_fullStr | Operando monitoring of the functional role of tetrahedral cobalt centers for the oxygen evolution reaction |
| title_full_unstemmed | Operando monitoring of the functional role of tetrahedral cobalt centers for the oxygen evolution reaction |
| title_short | Operando monitoring of the functional role of tetrahedral cobalt centers for the oxygen evolution reaction |
| title_sort | operando monitoring of the functional role of tetrahedral cobalt centers for the oxygen evolution reaction |
| url | https://doi.org/10.1038/s41467-025-55857-3 |
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