Preparation of a New Water Soluble Polynuclear Peroxide Complex of Pu(IV)

Abstract

International audienceDue to its acido-basic, complexing and redox properties, hydrogen peroxide has been widely used in nuclear research and industry. Particularly, this salt-free reagent has been highly considered for the stabilization of Pu(IV) in acid conditions and the precipitation of Pu peroxides as precursors for PuO$_2$ preparation. The addition of H$_2$O$_2$ to Pu(VI) acid solutions allows its conversion into Pu(V) which disproportionates and allows the accumulation of Pu(IV).[1] Further addition of H$_2$O$_2$ may lead to Pu(III), or a mixture of Pu(IV) and Pu(III), through the generation of a Pu(IV) peroxo complexe which decompose in acid conditions.[1,2] The continuous addition of H$_2$O$_2$ to Pu(IV) acid solutions leads to the progressive formation of a brown peroxo complex which turns red before insoluble plutonium peroxide precipitate.[2,3] The structure of these complexes which have been postulated in 1949 still remains under debate. Since, only one Pu peroxo structure has been recently proposed and concerned a dimeric molecular compound prepared in alkaline conditions.[4] The current study focuses on the behavior of Pu(IV) aqueous solutions in slightly acid conditions in the presence of hydrogen peroxide. We particularly describe the first observation of a water soluble polynuclear peroxo complex of Pu(IV) which has, up to our knowledge, never been reported in the literature