Neptunium carbonato complexes in aqueous solution; An Electrochemical, spectroscopic, and quantum chemical study

Ikeda, Atsushi  ; Tsushima, Satoru*; Takao, Koichiro*; Rossberg, A.*; Funke, H.*; Scheinost, A. C.*; Bernhard, G.*; Yaita, Tsuyoshi; Hennig, C.*

The electrochemical behavior and complex structure of Np carbonato complexes have been investigated in aqueous NaCO and NaCO/NaOH solutions at different oxidation states by using cyclic voltammetry, X-ray absorption spectroscopy, and density functional theory calculations. The end-member complexes of penta- and hexavalent Np in 1.5 M NaCO with pH = 11.7 have been determined as a transdioxo neptunyl tricarbonato complex, [NpO(CO)] ( = 5 for Np, and 4 for Np). In contrast, the electrochemical oxidation of Np in a highly basic carbonate solution of 2.0M NaCO/1.0M NaOH (pH 13) yielded a stable heptavalent Np complex of [Np O(OH)], indicating that the oxidation reaction from Np to Np in the carbonate solution involves a drastic structural rearrangement from the transdioxo configuration to a square-planar-tetraoxo configuration, as well as exchanging the coordinating anions from carbonate ions (CO) to hydroxide ions (OH).