Journal
INORGANIC CHEMISTRY
Volume 44, Issue 16, Pages 5641-5648Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic050130e
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A mesoporous silica-supported uranyl material (UaqO22+-Silica) was prepared by a co-condensation method. Our approach involves an I-M+S- scheme, where the electrostatic interaction between the anionic inorganic precursor (I-), surfactant (S-), and cationic mediator (M+) provides the basis for the stability of the composite material. The synthesis was carried out under acidic conditions, where the anionic sodium dodecyl sulfate provided the template for the uranyl cation and silicate to condense. Excitation with visible or near-UV light of aqueous suspensions of UaqO22+-Silica generates an excited state that decays with k(0) = 1.5 x 10(4) s(-1). The reaction of the excited state with aliphatic alcohols exhibits kinetic saturation and concentration-dependent kinetic isotope effects. For 2-propanol, the value of k(C3H7OH)/k(C3D7OH) decreases from 2.0 at low alcohol concentrations to 1.0 in the saturation regime at high alcohol concentrations. Taken together, the data describe a kinetic system controlled by chemical reaction at one extreme and diffusion at the other. At low [alcohol], the second-order rate constants for the reaction of silica-*UaqO22+ with methanol, 2-propanol, 2-butanol, and 2-pentanol are comparable to the rate constants obtained for these alcohols in homogeneous aqueous solutions containing H3PO4. Under slow steady-state photolysis in O-2-saturated suspensions, UaqO22+-Silica acts as a photocatalyst for the oxidation of alcohols with O-2.
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