Effect of H2O2 on the chemistry of f-element compounds in the + III and IV oxidation states in near-neutral and alkaline solutions

INOR 540

George S. Goff, georgeg@lanl.gov1, Lia F. Brodnax, lbrodnax@lanl.gov1, Michael R. Cisneros, mcisneros@lanl.gov2, Felicia L. Taw, ftaw@lanl.gov1, Kevin S. Williamson2, and Wolfgang H. Runde1. (1) Chemistry Division, Los Alamos National Laboratory, Mailstop J514, Los Alamos, NM 87545, (2) Chemistry Division, Los Alamos National Lab, Mailstop J514, Los Alamos, NM 87545
Understanding the molecular-level behavior of f-element compounds in near-neutral and alkaline solutions is essential for developing theoretical tools to predict solution behavior and separation efficiency in multi-metal, multi-ligand systems. This knowledge enables the development of innovative alkaline-based processes for spent nuclear fuel reprocessing. Adding H2O2 to alkaline solutions significantly alters the chemical and thermodynamic behavior of f-element compounds, including their oxidation state, coordination chemistry, and solubility. For example, small amounts of H2O2 rapidly reduces Pu(VI) to Pu(IV), forming a mixed-ligand complex in carbonate solutions. The first peroxo-carbonato Pu(IV) compound, Na8Pu2(O2)2(CO3)6•12H2O, with an architecture unprecedented among the 5f-elements, has been synthesized and structurally characterized. Peroxide can also undergo ligand-exchange reactions with Ln(III), and the resulting peroxo-carbonato complex has significantly lower solubility. We will report on the chemistry (structures and solution speciation) of +III and +IV f-element compounds in peroxide-carbonate solutions, and discuss experiments which revealed synergistic effects between Ln(III) and U(VI).