Atomic rare earths activate direct O-O coupling in manganese oxide towards electrocatalytic oxygen evolution
Activating the efficient electron transfer in oxygen evolution reaction (OER) by tuning the oxygen (O) electronic states near the Fermi level is essential to break the linear scaling limitation of OER intermediates. Herein, we construct a series of rare earth (RE) single atoms on MnO2 nanosheets wit...
| Autors principals: | , , , , , , , , , , , , , |
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| Altres autors: | |
| Format: | Journal Article |
| Idioma: | English |
| Publicat: |
2024
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| Accés en línia: | https://hdl.handle.net/10356/179143 |
| _version_ | 1826129956646682624 |
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| author | Li, Meng Wang, Xuan Zhang, Di Huang, Yujie Shen, Yijie Pan, Fei Lin, Jiaqi Yan, Wei Sun, Dongmei Huang, Kai Tang, Yawen Lee, Jong-Min Li, Hao Fu, Gengtao |
| author2 | School of Chemistry, Chemical Engineering and Biotechnology |
| author_facet | School of Chemistry, Chemical Engineering and Biotechnology Li, Meng Wang, Xuan Zhang, Di Huang, Yujie Shen, Yijie Pan, Fei Lin, Jiaqi Yan, Wei Sun, Dongmei Huang, Kai Tang, Yawen Lee, Jong-Min Li, Hao Fu, Gengtao |
| author_sort | Li, Meng |
| collection | NTU |
| description | Activating the efficient electron transfer in oxygen evolution reaction (OER) by tuning the oxygen (O) electronic states near the Fermi level is essential to break the linear scaling limitation of OER intermediates. Herein, we construct a series of rare earth (RE) single atoms on MnO2 nanosheets with modulated oxygen states by an effective and universal Ar plasma (P)-assisted strategy (P-RE SAs@MnO2, RE = Gd, La, Ce, Tm, and Lu) to investigate the origin of RE-enhanced OER performance. Taking P-Gd SAs@MnO2 as a representative, the atomically dispersed Gd atoms on MnO2 assist the construction of localized asymmetric [Gd−O−Mn] units, which induces electron accumulation at surrounding oxygen sites by introducing the polarized ionic Gd−O bond. As a result, the P-Gd SAs@MnO2 delivers impressive OER performance with low overpotential (281 mV@10 mA cm −2; ηj10), robust long-term stability, and optimized activation energy (Ea = 32.07 kJ mol−1 at ηj10), which are superior to RE-free MnO2, commercial RuO2, and most Mn-based catalysts. Similar enhanced OER performance can also be found for other P-RE SAs@MnO2 (RE = La, Ce, Tm, and Lu). X-ray absorption and in situ Raman spectroscopy unveil the preferred electron accumulation at Mn−O, promoting the formation of terminal MnIV=O intermediates in OER. Theoretical calculations demonstrate that the construction of [Gd−O−Mn] unit endows the surface lattice unsaturated O site with the labile property, which assists the direct formation of (O−O) dimer for circumventing the universal scaling relation applied by the formation of *OOH. This work opens up a new avenue for the design of transition metal oxides with modulated oxygen state to break the limitation of the adsorbate evolution mechanism during OER. |
| first_indexed | 2024-10-01T07:48:42Z |
| format | Journal Article |
| id | ntu-10356/179143 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T07:48:42Z |
| publishDate | 2024 |
| record_format | dspace |
| spelling | ntu-10356/1791432024-07-22T01:24:54Z Atomic rare earths activate direct O-O coupling in manganese oxide towards electrocatalytic oxygen evolution Li, Meng Wang, Xuan Zhang, Di Huang, Yujie Shen, Yijie Pan, Fei Lin, Jiaqi Yan, Wei Sun, Dongmei Huang, Kai Tang, Yawen Lee, Jong-Min Li, Hao Fu, Gengtao School of Chemistry, Chemical Engineering and Biotechnology Engineering Rare earth Lattice oxygen Activating the efficient electron transfer in oxygen evolution reaction (OER) by tuning the oxygen (O) electronic states near the Fermi level is essential to break the linear scaling limitation of OER intermediates. Herein, we construct a series of rare earth (RE) single atoms on MnO2 nanosheets with modulated oxygen states by an effective and universal Ar plasma (P)-assisted strategy (P-RE SAs@MnO2, RE = Gd, La, Ce, Tm, and Lu) to investigate the origin of RE-enhanced OER performance. Taking P-Gd SAs@MnO2 as a representative, the atomically dispersed Gd atoms on MnO2 assist the construction of localized asymmetric [Gd−O−Mn] units, which induces electron accumulation at surrounding oxygen sites by introducing the polarized ionic Gd−O bond. As a result, the P-Gd SAs@MnO2 delivers impressive OER performance with low overpotential (281 mV@10 mA cm −2; ηj10), robust long-term stability, and optimized activation energy (Ea = 32.07 kJ mol−1 at ηj10), which are superior to RE-free MnO2, commercial RuO2, and most Mn-based catalysts. Similar enhanced OER performance can also be found for other P-RE SAs@MnO2 (RE = La, Ce, Tm, and Lu). X-ray absorption and in situ Raman spectroscopy unveil the preferred electron accumulation at Mn−O, promoting the formation of terminal MnIV=O intermediates in OER. Theoretical calculations demonstrate that the construction of [Gd−O−Mn] unit endows the surface lattice unsaturated O site with the labile property, which assists the direct formation of (O−O) dimer for circumventing the universal scaling relation applied by the formation of *OOH. This work opens up a new avenue for the design of transition metal oxides with modulated oxygen state to break the limitation of the adsorbate evolution mechanism during OER. This work was financially supported by National Natural Science Foundation of China (22109073, 22379071, 22232004), Natural Science Foundation of Jiangsu Province (BK20221321), Jiangsu Specially Appointed Professor Plan, and Science and Technology Innovation Project for Overseas Researchers in Nanjing, JSPS KAKENHI (No. JP23K13703), and the Hirose Foundation. The authors are grateful for the supports from National and Local Joint Engineering Research Center of Biomedical Functional Materials and a project sponsored by the Priority Academic Program Development of Jiangsu Higher Education Institutions. H. Li acknowledges the Center for Computational Materials Science, Institute for Materials Research, Tohoku University for the use of MASAMUNE-IMR (202312-SCKXX-0203) and the Institute for Solid State Physics (ISSP) at the University of Tokyo for the use of their supercomputers. The authors acknowledge Beijing PARATERA Tech Co., Ltd. for providing HPC resources. 2024-07-22T01:24:53Z 2024-07-22T01:24:53Z 2024 Journal Article Li, M., Wang, X., Zhang, D., Huang, Y., Shen, Y., Pan, F., Lin, J., Yan, W., Sun, D., Huang, K., Tang, Y., Lee, J., Li, H. & Fu, G. (2024). Atomic rare earths activate direct O-O coupling in manganese oxide towards electrocatalytic oxygen evolution. Nano Energy, 128, 109868-. https://dx.doi.org/10.1016/j.nanoen.2024.109868 2211-2855 https://hdl.handle.net/10356/179143 10.1016/j.nanoen.2024.109868 2-s2.0-85195697072 128 109868 en Nano Energy © 2024 Elsevier Ltd. All rights are reserved, including those for text and data mining, AI training, and similar technologies. |
| spellingShingle | Engineering Rare earth Lattice oxygen Li, Meng Wang, Xuan Zhang, Di Huang, Yujie Shen, Yijie Pan, Fei Lin, Jiaqi Yan, Wei Sun, Dongmei Huang, Kai Tang, Yawen Lee, Jong-Min Li, Hao Fu, Gengtao Atomic rare earths activate direct O-O coupling in manganese oxide towards electrocatalytic oxygen evolution |
| title | Atomic rare earths activate direct O-O coupling in manganese oxide towards electrocatalytic oxygen evolution |
| title_full | Atomic rare earths activate direct O-O coupling in manganese oxide towards electrocatalytic oxygen evolution |
| title_fullStr | Atomic rare earths activate direct O-O coupling in manganese oxide towards electrocatalytic oxygen evolution |
| title_full_unstemmed | Atomic rare earths activate direct O-O coupling in manganese oxide towards electrocatalytic oxygen evolution |
| title_short | Atomic rare earths activate direct O-O coupling in manganese oxide towards electrocatalytic oxygen evolution |
| title_sort | atomic rare earths activate direct o o coupling in manganese oxide towards electrocatalytic oxygen evolution |
| topic | Engineering Rare earth Lattice oxygen |
| url | https://hdl.handle.net/10356/179143 |
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