The solution stability of plutonium(IV) oxo-hydroxo clusters is a central issue in actinide chemistry, with broad implications for fundamental coordination chemistry, the nuclear fuel cycle, and environmental migration. In this work, we investigate the long-term evolution of the hexanuclear Pu6O4(OH)412+ cluster stabilized by acetate ligands. Using ultraviolet-visible (UV-vis) absorption spectroscopy coupled with X-ray absorption (XAS) and small-angle X-ray scattering (SAXS) synchrotron techniques, we probed its structural transformation over nearly one year of aging. UV-vis and XAS analyses revealed a progressive loss of the molecular cluster signature accompanied by the emergence of low Pu-Pu coordination environments (CN = 5-6), characteristic of PuO2 colloidal nanoparticles. In contrast, SAXS measurements indicated a gradual increase in the apparent particle diameter of up to 10-15 nm, which is inconsistent with the formation of compact 2-3 nm PuO2 nanoparticles usually observed in aqueous solutions. The combined results most probably support a mechanism in which the hexameric cluster first converts into PuO2 primary colloids, which subsequently assemble into larger aggregates without crystallographic coalescence.
Muñoz et al. (Wed,) studied this question.