Abstract
Recent studies on the electrocatalytic oxygen transfer from water to organic compounds have gained significant attention due to their sustainability and selectivity. However, the direct coactivation of inert hydrocarbons and water typically requires high oxidation potentials, leading to oxygen evolution reactions and low Faradaic efficiencies. Herein, a Ni-activated tungsten-oxygen covalency anode is designed for the efficient oxygen transfer from water to benzylic C(sp3)–H bonds via a Ni-regulated interfacial water structure between the anode and electrolyte. Both experimental and theoretical results reveal the critical role of W–O covalency sites with Ni-heteroatoms for boosting efficient oxygen transfer via breaking the dense interfacial hydrogen bond network and inhibiting the undesired oxygen evolution reactions, facilitating the coactivation of oxygen species and C(sp3)–H bonds. Thus, a Faradaic efficiency of > 56% in a water-involved system has been achieved. This work provides important insight into designing electrocatalytic systems for inert C–H oxidation.
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All the relevant data are included in this paper and its Supplementary Information. The data that support the findings of this study are available from the corresponding authors upon request. Source data are provided with this paper.
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Acknowledgements
This work was supported by Shanghai Science and Technology Committee (23XD1421800 for X.-H. L.), Shanghai Shuguang Program (21SG12 for X.-H. L.), State Key Laboratory of Synergistic Chem-Bio Synthesis (sklscbs202551 for X.-H. L.), and Shanghai Municipal Science and Technology Major Project (J.-S. C.).
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X.-H. L., B.-L. L., and X. L. designed the experiments. B.-L. L. planned and performed catalyst synthesis, conducted performance tests and analyzed data. B.-L. L. finished the theoretical calculation. D.-H. Y. contributed to the substrate scope section. Q.-Y. L. and S.-N. Z. helped to analyze the theoretical calculation. X.-H. L. and B.-L. L. cowrote the original manuscript. X.-H. L. and J.-S. C. oversaw all the research phases. All of the authors discussed the results and commented on the paper.
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Leng, BL., Lin, X., Dong, HY. et al. Regulating interfacial water for oxygen transfer to benzylic C(sp3)–H bonds via Ni-activated tungsten-oxygen covalency. Nat Commun (2026). https://doi.org/10.1038/s41467-026-69054-3
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DOI: https://doi.org/10.1038/s41467-026-69054-3
