Breaking linear scaling relationships in oxygen evolution via dynamic structural regulation of active sites
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-Fe<sub>2</sub> 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.
Authors
- Shibo Xi (ORCID: https://orcid.org/0000-0002-8521-3237)
- Xiaoxu Zhao (ORCID: https://orcid.org/0000-0001-9746-3770)
- Peng Chen (ORCID: https://orcid.org/0000-0003-3730-1846)
- Hong Bin Yang (ORCID: https://orcid.org/0000-0002-7834-4706)
- Zheye Zhang (ORCID: https://orcid.org/0000-0002-2268-5050)
- Zhongxin Chen (ORCID: https://orcid.org/0000-0001-6153-5381)
- Bin Liu (ORCID: https://orcid.org/0000-0002-4685-2052)
- Xiaojiang Yu (ORCID: https://orcid.org/0000-0002-7044-6417)
- Xiao Chi (ORCID: https://orcid.org/0000-0002-9728-8770)
- Yang‐Gang Wang (ORCID: https://orcid.org/0000-0002-0582-0855)
- Hongyan Zhao (ORCID: https://orcid.org/0000-0002-1057-6287)
Institutions
- Agency for Science, Technology and Research (SG)
- National University of Singapore (SG)
- City University of Hong Kong (HK)
- Nanyang Technological University (SG)
- Peking University (CN)
- Southern University of Science and Technology (CN)
- Suzhou University of Science and Technology (CN)
- Chinese University of Hong Kong, Shenzhen (CN)
Publication Details
- Journal
- Nature Communications
- Published
- 2025-02-03
- DOI
- https://doi.org/10.1038/s41467-024-55150-9
- Citations
- 62
- Primary Topic
- Electrochemical Analysis and Applications
- Type
- article
- Field-Weighted Citation Impact
- 31.94
Funders
- City University of Hong Kong
- National University of Singapore
- National Natural Science Foundation of China
- Science, Technology and Innovation Commission of Shenzhen Municipality
- National Supercomputing Centre Singapore