First observation of [Pu6(OH)4O4]12+ cluster during the hydrolytic formation of PuO2 nanoparticles using H/D kinetic isotope effect

Manon Cot-Auriol; Matthieu Virot; Thomas Dumas; Olivier Diat; Denis Menut; Philippe Moisy; Sergey I Nikitenko

doi:10.1039/d2cc04990b

First observation of [Pu₆(OH)₄O₄]¹²⁺ cluster during the hydrolytic formation of PuO₂ nanoparticles using H/D kinetic isotope effect

Chem Commun (Camb). 2022 Nov 24;58(94):13147-13150. doi: 10.1039/d2cc04990b.

Authors

Manon Cot-Auriol¹, Matthieu Virot¹, Thomas Dumas², Olivier Diat¹, Denis Menut³, Philippe Moisy², Sergey I Nikitenko¹

Affiliations

¹ ICSM, Univ Montpellier, CEA, CNRS, ENSCM, Marcoule, France. matthieu.virot@cea.fr.
² CEA, DES, ISEC, DMRC, Univ Montpellier, Marcoule, France.
³ Synchrotron SOLEIL, L'Orme des Merisiers, Départementale 128, 91190 Saint Aubin, France.

PMID: 36349890
DOI: 10.1039/d2cc04990b

Abstract

New insights are provided about the formation mechanism of PuO₂ nanoparticles (NPs) by investigating an unprecedented kinetic isotope effect observed during their hydrolytic synthesis in H₂O or D₂O 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 PuO₂ NPs (synchrotron SAXS/XAS), is further revealed indicating that their formation is controlled by H-transfer reactions occurring during hydroxo to oxo-bridge conversions.