First observation of [Pu 6 (OH) 4 O 4 ] 12+ cluster during the hydrolytic formation of PuO 2 nanoparticles using H/D kinetic isotope effect.

Authors :: Cot-Auriol M
Virot M
Dumas T
Diat O
Menut D
Moisy P
Nikitenko SI
Source :: Chemical communications (Cambridge, England) [Chem Commun (Camb)] 2022 Nov 24; Vol. 58 (94), pp. 13147-13150. Date of Electronic Publication: 2022 Nov 24.
Publication Year :: 2022
Abstract: New insights are provided about the formation mechanism of PuO <subscript>2</subscript> nanoparticles (NPs) by investigating an unprecedented kinetic isotope effect observed during their hydrolytic synthesis in H <subscript>2</subscript> O or D <subscript>2</subscript> O and attributed to OH/OD zero point energy difference. The signature of a Pu(IV) oxo-hydroxo hexanuclear cluster, appearing as an important intermediate during the formation of the 2 nm PuO <subscript>2</subscript> NPs (synchrotron SAXS/XAS), is further revealed indicating that their formation is controlled by H-transfer reactions occurring during hydroxo to oxo-bridge conversions.

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