The oxygen evolving catalyst [Ru(4)(μ-OH)(2)(μ-O)(4)(H(2)O)(4)(γ-SiW(10)O(36))(2)](10-) effects H(2)O(2) dismutation at rates (k = 36.8 ± 1.4 M(-1) s(-1)), one/two order of magnitude higher compared to related tetra-substituted Cu, Fe, Mn, Ni and even Co polyoxometalates, thus providing localised oxygen gas bursts to power nano-propulsion of composite materials.

Hybrid fluoropolymeric membranes with 25% loading of the fluorous-tagged (RfN)4W10O32 effect the solvent-free photooxygenation of benzylic C-H bonds with up to 6100 TONs in 4 hours.

Anchoring terminal octenyl tails on molecular polyoxotungstates yield polymerizable organic-inorganic monomers with formula [{CH(2)=CH(CH(2))(6)Si}(x)O(y)SiW(w)O(z)](4-) [x = 2, w = 11, y = 1, z = 39 (1); x = 2, w = 10, y = 1, z = 36 (2); and x = 4, w = 9, y = 3, z = 34 (3)]. These molecular hybrids can use aqueous hydrogen peroxide to catalyze the selective oxidation of organic sulfides in CH(3)CN. Copolymerization of 1-3 with methyl methacrylate and ethylene glycol dimethacrylate leads to porous materials with a homogeneous distribution of the functional monomers, as indicated by converging evidence from FTIR spectroscopy and electronic microscopy. The catalytic polymers activate hydrogen peroxide for oxygen transfer, as demonstrated by the quantitative and selective oxidation of methyl p-tolyl sulfide, which was screened as model substrate. The hybrid material containing monomer 2 was also tested in n-octane to evaluate its potential for the oxidation and removal of dibenzothiophene, a well-known gasoline contaminant.

The incorporation of decatungstate in polymeric membranes provides new heterogeneous photocatalysts for the oxidation of organic substrates under oxygen atmosphere at 25°C. Photocatalytic membranes have been prepared yielding polymeric films with a high thermal, chemical and mechanical stability (PVDF, PDMS, Hyflon). Surface spectroscopy techniques including transmittance and reflectance UV-Vis and FT-IR have been used to assess the photocatalyst integrity within the polymeric support. Catalyst screening has been performed under both homogeneous and heterogeneous photooxygenation conditions. The photocatalyst activity has been evaluated in terms of the substrate conversion, turnover numbers, and recycling experiments. A membrane induced selectivity behavior has been evidenced by comparison with homogeneous oxidations.

Fluorophilic polyoxotungstates perform the selective epoxidations of internal and terminal double bonds by hydrogen peroxide (H2O2) activation in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), under mild temperature conditions. A hybrid synergy of supramolecular interactions, involving the inorganic cluster and the fluorinated solvent, is envisaged to boost H2O2 activation and the oxygen transfer mechanism. 1,2-Epoxides have been obtained with >99% selectivity and 98% yield at T = 40-70 °C.