Synergy of Rectangular Truncated Highly Reactive Facets of the Functional Heterometallic Oxo Cage for Enhanced Decomposition of Paraoxon

Here, we synthesize a highly porous (17.2 nm, pore volume = 0.1753 cm³/g) infinite 3D coordination network of hexanuclear heterometallic mixed metallic oxo cage {MoTI₅O₂} in which the Ti and Mo centers are interconnected via edge and corner sharing MO₆ polyhedra and demonstrate its performance to destroy the organophosphorus-based nerve simulants. The superior performance arises from a synergistic interplay of multiple pathways; defect-engineered facets create unsaturated active sites that facilitate reduction processes and stabilize oxygen vacancies, while ROS-active low-index facets promote oxidative degradation through enhanced adsorption. The strongly negative surface potential (ζ = -40 mV) accelerates hydrolytic cleavage via a direct SN² pathway (kobs = 5.41 × 10⁻⁵ s⁻¹) driven by carboxylate functionalities coordinated to Ti centers, with nanoconfined water further enhancing P-O bond cleavage. Importantly, Mo⁵⁺ centers exhibit dual functionality by participating in oxidative hydrolysis and mimicking nitrogenase-like activity to convert p-nitrophenoxide to p-aminophenoxide ions. The confined architecture promotes efficient hole trapping, suppresses charge recombination, and enhances charge-carrier mobility, while Mo⁶⁺ incorporation into the TiO₂ lattice broadens light absorption and narrows the band gap to 2.66 eV in the oxo-bridged (F)nMo-μ3/2O-Tn heterometallate. Interestingly, the water-dispersible magnetic core-shell system, (F)nMo-μ₃/₂O-Tn@Fe₃O₄, exhibits high selectivity toward phosphate moieties, enabling efficient organophosphorus removal via magnetic separation. Overall, this work establishes a powerful multimodal platform for the rapid, selective, and practical decontamination of organophosphates from environmental systems.