Synthesis and Catalytic Oxidation Studies of a Novel Keggin-Type Complex Catalyst [(CH2)5NH2]5PMo10V2O40
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Developing efficient and robust polyoxometalate catalysts is highly desirable for green organic oxidation. In this work, we synthesized a novel organic-inorganic hybrid Keggin-type complex, [(CH 2 ) 5 NH 2 ] 5 PMo 10 V 2 O 40 , via the assembly of phosphomolybdovanadic acid and piperidine. Structural analyses using FT-IR and XRD confirmed that the parent [PMo 10 V 2 O 40 ] 5− framework remains fully intact. Meanwhile, the intercalation of piperidinium cations expands the crystal lattice and induces a unique monoclinic supramolecular architecture. Thermogravimetric analysis revealed a significant enhancement in thermal stability, with the material resisting decomposition up to 433°C. We evaluated the practical utility of this complex in the selective oxidation of benzaldehyde to benzoic acid using aqueous H 2 O 2 . Under mild optimized conditions (75°C, 2.5 h), the catalyst achieved an 87% yield with absolute selectivity. This exceptional performance originates from two distinct structural advantages. The V/Mo heterometallic interaction inherently boosts the overall redox capacity, facilitating rapid oxidant activation. Concurrently, the organic cations construct a localized hydrophobic microenvironment within the lattice. This specific pocket selectively adsorbs the organic substrate and repels excess hydrophilic oxidants, thereby accelerating the reaction while effectively suppressing overoxidation.
