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

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 e

SUBMITTER: Tian M 

PROVIDER: S-EPMC12917289 | biostudies-literature | 2026 Jan

REPOSITORIES: biostudies-literature