ABSTRACT Selective separation of trivalent actinide ions, An(III), from trivalent actinide ions, Ln(III), has been of great importance and considerable challenge in terms of the overall nuclear fuel cycle strategy. The construction of the hard-soft synergistic extraction system, commonly S containing-O containing ligands, aims to achieve the effective separation of the two metal ions. Nevertheless, the precise mechanism by which this system extracts metal ions remains the subject of controversy. Herein, the complexation of Nd(III) with bis(2,4,4-trimethylpentyl)dithiophosphinic acid (HL) and tributyl phosphate (TBP) has been investigated with spectroscopy and extraction experiments under different conditions to clarify the mechanisms in synergistic extraction. Five complex species, NdL3(HL)(TBP), NdL2(NO3)(TBP)3, NdL3(H2O)2(TBP), NdL3(H2O)(TBP)2, and NdL3(TBP)3, are identified in the synergistic extraction system, their molar absorption spectra are deconvoluted, and the corresponding extraction equilibrium constants are determined. In addition, a complex species of Nd(III) fully coordinated by TBP, NdL3(TBP)n (n ≥ 6), is found in titrations of organic solution containing NdL3(TBP)3 with more TBP, but it is not found in synergistic extraction. Furthermore, Density Functional Theory (DFT) is employed to confirm the stability of the complexes. Investigation of the mechanism of this system will facilitate the acquisition of further insights into the selection of O-containing ligands and the development of synergistic extraction process for the separation of An(III) and Ln(III).
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