Breaking linear scaling relationships in oxygen evolution via dynamic structural regulation of active sites
Abstract The universal linear scaling relationships between the adsorption energies of reactive intermediates limit the performance of catalysts in multi-step catalytic reactions. Here, we show how these scaling relationships can be circumvented in electrochemical oxygen evolution reaction by dynami...
Saved in:
| Main Authors: | , , , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2025-02-01
|
| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-55150-9 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1823861825334149120 |
|---|---|
| author | Zheye Zhang Hongyan Zhao Shibo Xi Xiaoxu Zhao Xiao Chi Hong Bin Yang Zhongxin Chen Xiaojiang Yu Yang-Gang Wang Bin Liu Peng Chen |
| author_facet | Zheye Zhang Hongyan Zhao Shibo Xi Xiaoxu Zhao Xiao Chi Hong Bin Yang Zhongxin Chen Xiaojiang Yu Yang-Gang Wang Bin Liu Peng Chen |
| author_sort | Zheye Zhang |
| collection | DOAJ |
| description | Abstract The universal linear scaling relationships between the adsorption energies of reactive intermediates limit the performance of catalysts in multi-step catalytic reactions. Here, we show how these scaling relationships can be circumvented in electrochemical oxygen evolution reaction by dynamic structural regulation of active sites. We construct a model Ni-Fe2 molecular catalyst via in situ electrochemical activation, which is able to deliver a notable intrinsic oxygen evolution reaction activity. Theoretical calculations and electrokinetic studies reveal that the dynamic evolution of Ni-adsorbate coordination driven by intramolecular proton transfer can effectively alter the electronic structure of the adjacent Fe active centre during the catalytic cycle. This dynamic dual-site cooperation simultaneously lowers the free energy change associated with O–H bond cleavage and O–O bond formation, thereby disrupting the inherent scaling relationship in oxygen evolution reaction. The present study not only advances the development of molecular water oxidation catalysts, but also provides an unconventional paradigm for breaking the linear scaling relationships in multi-intermediates involved catalysis. |
| format | Article |
| id | doaj-art-a18f382c02b24db29745369feeadf680 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-02-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-a18f382c02b24db29745369feeadf6802025-02-09T12:44:47ZengNature PortfolioNature Communications2041-17232025-02-0116111210.1038/s41467-024-55150-9Breaking linear scaling relationships in oxygen evolution via dynamic structural regulation of active sitesZheye Zhang0Hongyan Zhao1Shibo Xi2Xiaoxu Zhao3Xiao Chi4Hong Bin Yang5Zhongxin Chen6Xiaojiang Yu7Yang-Gang Wang8Bin Liu9Peng Chen10School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological UniversityDepartment of Chemistry and Guangdong Provincial Key Laboratory of Catalytic Chemistry, Southern University of Science and TechnologyInstitute of Sustainability for Chemicals, Energy and Environment (ISCE2), Agency for Science, Technology and Research (A*STAR)School of Materials Science and Engineering, Peking UniversityDepartment of Physics, National University of SingaporeSchool of Materials Science and Engineering, Suzhou University of Science and TechnologySchool of Science and Engineering, The Chinese University of Hong KongSingapore Synchrotron Light Source, National University of SingaporeDepartment of Chemistry and Guangdong Provincial Key Laboratory of Catalytic Chemistry, Southern University of Science and TechnologyDepartment of Materials Science and Engineering, City University of Hong KongSchool of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological UniversityAbstract The universal linear scaling relationships between the adsorption energies of reactive intermediates limit the performance of catalysts in multi-step catalytic reactions. Here, we show how these scaling relationships can be circumvented in electrochemical oxygen evolution reaction by dynamic structural regulation of active sites. We construct a model Ni-Fe2 molecular catalyst via in situ electrochemical activation, which is able to deliver a notable intrinsic oxygen evolution reaction activity. Theoretical calculations and electrokinetic studies reveal that the dynamic evolution of Ni-adsorbate coordination driven by intramolecular proton transfer can effectively alter the electronic structure of the adjacent Fe active centre during the catalytic cycle. This dynamic dual-site cooperation simultaneously lowers the free energy change associated with O–H bond cleavage and O–O bond formation, thereby disrupting the inherent scaling relationship in oxygen evolution reaction. The present study not only advances the development of molecular water oxidation catalysts, but also provides an unconventional paradigm for breaking the linear scaling relationships in multi-intermediates involved catalysis.https://doi.org/10.1038/s41467-024-55150-9 |
| spellingShingle | Zheye Zhang Hongyan Zhao Shibo Xi Xiaoxu Zhao Xiao Chi Hong Bin Yang Zhongxin Chen Xiaojiang Yu Yang-Gang Wang Bin Liu Peng Chen Breaking linear scaling relationships in oxygen evolution via dynamic structural regulation of active sites Nature Communications |
| title | Breaking linear scaling relationships in oxygen evolution via dynamic structural regulation of active sites |
| title_full | Breaking linear scaling relationships in oxygen evolution via dynamic structural regulation of active sites |
| title_fullStr | Breaking linear scaling relationships in oxygen evolution via dynamic structural regulation of active sites |
| title_full_unstemmed | Breaking linear scaling relationships in oxygen evolution via dynamic structural regulation of active sites |
| title_short | Breaking linear scaling relationships in oxygen evolution via dynamic structural regulation of active sites |
| title_sort | breaking linear scaling relationships in oxygen evolution via dynamic structural regulation of active sites |
| url | https://doi.org/10.1038/s41467-024-55150-9 |
| work_keys_str_mv | AT zheyezhang breakinglinearscalingrelationshipsinoxygenevolutionviadynamicstructuralregulationofactivesites AT hongyanzhao breakinglinearscalingrelationshipsinoxygenevolutionviadynamicstructuralregulationofactivesites AT shiboxi breakinglinearscalingrelationshipsinoxygenevolutionviadynamicstructuralregulationofactivesites AT xiaoxuzhao breakinglinearscalingrelationshipsinoxygenevolutionviadynamicstructuralregulationofactivesites AT xiaochi breakinglinearscalingrelationshipsinoxygenevolutionviadynamicstructuralregulationofactivesites AT hongbinyang breakinglinearscalingrelationshipsinoxygenevolutionviadynamicstructuralregulationofactivesites AT zhongxinchen breakinglinearscalingrelationshipsinoxygenevolutionviadynamicstructuralregulationofactivesites AT xiaojiangyu breakinglinearscalingrelationshipsinoxygenevolutionviadynamicstructuralregulationofactivesites AT yanggangwang breakinglinearscalingrelationshipsinoxygenevolutionviadynamicstructuralregulationofactivesites AT binliu breakinglinearscalingrelationshipsinoxygenevolutionviadynamicstructuralregulationofactivesites AT pengchen breakinglinearscalingrelationshipsinoxygenevolutionviadynamicstructuralregulationofactivesites |