Insights into the structure and thermal stability of uranyl aluminate nanoparticles

Ultrasonically assisted hydrolytic precipitation of U(VI) in the presence of mesoporous alumina followed by thermal treatment of solid precursor allowed to obtain crystallized uranyl aluminate (URAL) nanoparticles (NPs) dispersed in alumina matrix. Effect of U(VI) concertation and calcination temperature on the yield of URAL NPs was studied using XRD, XAFS and HRTEM techniques. At 800°C, URAL NPS (d≈5 nm) are formed only for low uranium loading of about 5 wt% whereas for higher content of uranium, larger U3O8 NPs (d≈20 nm) were identified as a principal uranium specie. At 500°C, URAL NPs are formed even for 25 wt% of uranium. U LIII edge EXAFS spectra pointed out that uranyl cation in URAL is coordinated by bidentate aluminate groups. Presumably URAL is formed during the heating of 2UO3·NH3·2H2O/AlO(OH) precursor. However, high temperature and larger content of uranium promote URAL transformation to more thermodynamically stable U3O8 oxide. This process is accompanied by uranium NPs growing via Ostwald ripening mechanism.