The application of HEXS and HERFD XANES for accurate structural characterization of actinide nanomaterials: application to ThO₂

Autor: Amidani, L., Vaughan, G. B. M., Plakhova, T. V., Romanchuk, A. Y., Gerber, E., Svetogorov, R., Weiß, S., Joly, Y., Kalmykov, S. N., Kvashnina, K.
Jazyk: angličtina
Rok vydání: 2021
Předmět:
Zdroj: Chemistry-A European Journal 27(2021)1, 252-263
Popis: Structural characterization of actinide nanoparticles (NPs) is of primary importance and hard to achieve, especially for non‐homogeneous samples with NPs below 3 nm. By combining High Energy X‐ray Scattering (HEXS) and High‐Energy‐Resolution Fluorescence Detected X‐ray Near‐Edge Structure (HERFD XANES), we characterized for the first time both short‐ and medium‐range order of ThO₂ NPs obtained by chemical precipitation. With this methodology, a novel insight into the structure of NPs at different steps of their formation process is achieved. The Pair Distribution Function (PDF) reveals a high concentration of ThO₂ small units similar to Th hexamer clusters mixed with 1 nm ThO₂ NPs in the initial steps of formation. Drying the precipitates at ⁓150 °C promotes recrystallization of the smallest units into more thermodynamically stable ThO₂ NPs. HERFD XANES at Th M₄ edge, a direct probe of the f states, shows variations that we correlate to the break of the local symmetry around Th atoms, which most likely concerns surface atoms. Together, HEXS and HERFD are a powerful methodology to investigate actinide NPs and their formation mechanism.
Databáze: OpenAIRE