Abstract
Understanding the structural dynamics of ligands and their interaction with catalytic centres under reaction conditions remains a fundamental challenge, yet it is essential for catalyst design. Here we reveal an in situ transformation of Ni–Fe hydroxide into a stable superoxo-hydroxide phase, which is accompanied by the formation of lattice O–O (Olatt–Olatt) ligands, as demonstrated using operando 18O-labelling spectroelectrochemistry and machine-learning-assisted global optimization. By correlating the intrinsic activity of Fe with the Olatt–Olatt concentration across a series of Fe-incorporated transition-metal hydroxides and oxides, we demonstrate that Olatt–Olatt triggers Fe activation for oxygen evolution electrocatalysis—a finding further supported by first-principles calculations. Oxygen production proceeds via an adsorbate evolution mechanism, and the enhanced reaction kinetics stem from the lowered activation energy at surface Fe sites in the newly formed superoxo-hydroxide structure. This work offers a strategic framework for designing high-performance Fe-incorporated electrocatalysts and underscores the pivotal role of ligand dynamics in activating catalytic centres.
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Data availability
The data supporting the findings of this study are available within this article and its Supplementary Information. The raw data files in another format are available from the corresponding authors upon reasonable request. Source data are provided with this paper.
Code availability
The software code of LASP and G-NN potential used within the article is available from the corresponding authors upon request or at http://www.lasphub.com.
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Acknowledgements
This research was supported by the National Key R&D Program of China (grant no. 2022YFA1505200), National Natural Science Foundation of China (grant nos. 21972023, 22072030, 22022301, 22272029 and 22472036), Science and Technology Commission of Shanghai Municipality (grant nos. 22520711100, 23ZR1406900 and 2024ZDSYS02) and the Fundamental Research Funds for the Central Universities (grant no. 20720220008).
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L.Z. designed and conceived the experiment. G.S. fabricated the electrodes and carried out electrochemical and in situ spectroscopy characterizations. T.L. and Q.X. performed in situ XRD measurements. C.Y., H.G., H.T., S. Zhao, C.Z., Y.S. and J.W. assisted with other physical characterizations. X.L. and P.-C.C. conducted the TEM characterization. Jiong Li and S. Zhang helped on the XAS data acquisition. J.S. and K.H.L.Z. worked on the thin-film catalyst preparation. Jili Li, Y.-F.L. and Z.-P.L. contributed to the DFT calculations. G.S., Jili Li, Y.-F.L and L.Z. cowrote the paper. All authors discussed the results and provided feedback on the paper.
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Crystal structures of key OER intermediate states.
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Shi, G., Li, J., Lu, T. et al. Lattice O–O ligands in Fe-incorporated hydroxides enhance water oxidation electrocatalysis. Nat. Chem. 17, 1607–1614 (2025). https://doi.org/10.1038/s41557-025-01898-6
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DOI: https://doi.org/10.1038/s41557-025-01898-6
