Abstract
Co(IV) = O-mediated Fenton-like processes show great potential for water remediation but are fundamentally limited by the “oxo-wall” effect, which imposes prohibitive activation energies for Co(IV) = O bond formation and stabilization. Herein, by unifying thermodynamic analysis with the “oxo-wall” constraint mechanism, we establish the comprehensive theoretical framework for Co(IV) = O-dominated non-radical Fenton-like oxidation pathways. We design a Ce-Co tetra-(4-carboxyphenyl) porphyrin framework (Ce-Co TCPP), where Ce(IV)-based oxide linkers induce long-range electronic modulation, enhancing electronic delocalization at Co–N4 sites. This significantly reduces electron occupancy in Co–O antibonding orbitals, thereby effectively circumventing “oxo-wall” constraints. Combined experimental and computational analyses confirm that Co(IV) = O species dominate in the Ce-Co TCPP/peroxymonosulfate (PMS) system, where synergistic electron transfer and proton transfer processes significantly lower activation barriers. Practically, the lamellar Ce-Co TCPP membrane/PMS system achieves desirable water permeability (126.97 L·m−2·h−1·bar−1 (LMHB)), high pollutant degradation efficiency (0.0717 ms−1), robust anti-interference capability, and long-term operational stability (95 h), which can be attributed to the shortened mass transport pathways and the approximately 1000-fold enrichment of Co(IV) = O complexes within membrane nanoconfined channels. This work offers an innovative strategy for sustainable Co(IV) = O-mediated advanced oxidation processes in water treatment.
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Data availability
The data generated in this study are provided in the Supplementary Materials/source data file. All the raw data relevant to the study are available from the corresponding author upon request. Source data are provided with this paper. The optimized DFT computational models and molecular dynamics trajectories generated in this study are publicly available on GitHub: https://github.com/JomerMatirays/Breakingtheoxo-wallforCo-IV--oxospeciesandtheirnanoconfinedcatalyticperformancewithinCe-Comembrane/. These data are also permanently archived in the Zenodo repository (https://doi.org/10.5281/zenodo.17895247). Source data are provided with this paper.
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Acknowledgements
The research was supported by the National Natural Science Foundation of China (52170041, Z.Z.), Tsinghua SIGS Cross-disciplinary Research and Innovation Fund (JC2022006, Z.Z.), the Committee of Science and Technology Innovation of Shenzhen (JCYJ20230807111705011, Z.Z.), and the Guangdong Natural Science Fund for Distinguished Young Scholars (2024B1515020085, Z.Z.).
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Z.Z. conceived the project. M.T. synthesized and characterized the nanosheets and membranes and performed the catalytic activity experiments. L.L. and Z.C. helped with experiments and result analysis. C.Y. performed the XAFS analysis. H.Z. and Y.L. performed the theoretical calculations. M.T. and Z.Z. analyzed the results and wrote the manuscript. Z.Z. revised the manuscript. All authors discussed the results and commented on the manuscript.
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Tian, M., Zhang, H., Liu, Y. et al. Breaking the oxo-wall for Co(IV)-oxo species and their nanoconfined catalytic performance within Ce-Co lamellar membrane. Nat Commun (2026). https://doi.org/10.1038/s41467-026-68471-8
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DOI: https://doi.org/10.1038/s41467-026-68471-8
