Breaking the oxo-wall for Co(IV)-oxo species and their nanoconfined catalytic performance within Ce-Co lamellar membrane

作者：Mengtao Tian, Hongyi Zhang, Yi Liu, Lei Li, Can Yu, Zhen Chen, Zhenghua Zhang · 发表于：Nature Communications · 年份：2026 · DOI：10.1038/s41467-026-68471-8 · 被引用次数：13 · 研究领域：Advanced oxidation water treatment、Electrocatalysts for Energy Conversion、Advanced battery technologies research

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 f...