The Application of HEXS and HERFD XANES for Accurate Structural Characterisation of Actinide Nanomaterials: The Case of ThO2.

Abstract

The structural characterisation of actinide nanoparticles (NPs) is of primary importance and hard to achieve, especially for non‐homogeneous samples with NPs less than 3 nm. By combining high‐energy X‐ray scattering (HEXS) and high‐energy‐resolution fluorescence‐detected X‐ray absorption near‐edge structure (HERFD XANES) analysis, we have characterised for the first time both the short‐ and medium‐range order of ThO2 NPs obtained by chemical precipitation. By using this methodology, a novel insight into the structures of NPs at different stages of their formation has been achieved. The pair distribution function revealed a high concentration of ThO2 small units similar to thorium hexamer clusters mixed with 1 nm ThO2 NPs in the initial steps of formation. Drying the precipitates at around 150 °C promoted the recrystallisation of the smallest units into more thermodynamically stable ThO2 NPs. HERFD XANES analysis at the thorium M4 edge, a direct probe for f states, showed variations that we have correlated with the breakdown of the local symmetry around the thorium atoms, which most likely concerns surface atoms. Together, HEXS and HERFD XANES are a powerful methodology for investigating actinide NPs and their formation mechanism.