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.
Miri et al. (Mon,) studied this question.