Insight into the structure-property relationship of UO2 nanoparticles

Fast chemical deposition of uranium(IV) under reducing conditions at pH 8-11 results in the formation of highly crystalline UO2 nanoparticles (NPs) with sizes of 2-3 nm, which is similar to the formation mechanism of PuO2 NPs. UO2 NPs are characterized by various microscopic and spectroscopic techniques including high energy transmission electron microscopy (HRTEM), high energy resolution fluorescence detection (HERFD) X-ray absorption spectroscopy and extended X-ray absorption fine structure (EXAFS) spectroscopy. Despite U(IV) being the dominant oxidation state of the freshly prepared UO2 NPs, they readily oxidize to U4O9 with time and under the X-ray beam. This oxidation of NPs is accompanied by their growth in size to 6 nm. The high tendency of UO2 NPs towards oxidation differs from PuO2 NPs’ behaviour due to the extremely high stability of Pu(IV) and much lower stability of oxidized Pu(V/VI) as compared to U(V/VI).