A Novel Metastable Pentavalent Plutonium Solid Phase on the Pathway from Aqueous Plutonium(VI) to PuO2 Nanoparticles

Here we provide evidence that the formation of PuO2 nanoparticles from oxidized PuVI under alkaline conditions proceeds through the formation of an intermediate PuV solid phase, similar to NH4PuO2CO3, which is stable over a period of several months. For the first time, state‐of‐the‐art experiments at Pu M4 and at L3 absorption edges combined with theoretical calculations unambiguously allow to determine the oxidation state and the local structure of this intermediate phase. Solid proof: The formation of a novel pentavalent plutonium solid phase was observed on the pathway from aqueous PuVI to PuO2 nanoparticles by applying a high energy resolution fluorescence detection method at the Pu M4 and L3 edges and electronic structure calculations.