Campbell Tom, Newton Mark A, Boyd Vicky, Lee Darren F, Evans John
School of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, United Kingdom.
J Phys Chem B. 2005 Feb 24;109(7):2885-93. doi: 10.1021/jp0404394.
A range of uranium oxide-based catalysts, derived from UO2(NO3)2.6H2O and UCl4 precursors, and supported on gamma-Al2O3, SiO2 and mesoporous H1SiO2, have been synthesized and then characterized using the following methods: isothermal nitrogen adsorption/desorption measurements, diffuse reflectance infrared spectroscopy (DRIFTS), gas titration of surface hydroxyl groups using Grignard reagents, U L(III) extended X-ray absorption fine structure (EXAFS), powder X-ray diffraction (PXRD), and thermogravimetric and differential thermal analysis. Brij76-templated H1SiO2 mesoporous silicas are found to be essentially stable under flowing oxygen after 16 h at 1073 K. At temperatures above this, however, extensive structural collapse, together with extensive dehydroxylation, ensues. Titration of the accessible hydroxyl group concentrations shows that in these materials the density of OH groups is considerably lower than in their amorphous counterparts. The adsorption of uranyl nitrate onto these dispersants results in a supported, and partially dehydrated, phase of the parent molecule with little obvious structural distortion; however, the adsorption of UCl4 leads to a complex adstructure which may best be described as U(O)2Cl2. The subsequent formation of the uranium oxide phase, nominally active for the oxidation of CO and selective reduction of NO (generally accepted to be U3O8), is found to be a considerable function of both the precursor and support system employed. Calcination of such systems to 1073 K results in extensive extrusion of the supported uranium phase from mesoporous supports, resulting in the formation of very large orthorhombic U3O8 domains. PXRD, however, shows that on amorphous SiO2 and gamma-Al2O3 similar treatment results in the formation of a hexagonal phase of U3O8. The formation of U3O8 is found to be promoted in mesoporous systems and by the presence of Cl in the catalyst make up. Some evidence is also found that suggests that a persistence of Cl limits the growth of U3O8 domains.
