Theoretical insights into the possible applications of amidoxime-based adsorbents in neptunium and plutonium separation

Efficient separation of neptunium and plutonium from spent nuclear fuel is essential for advanced nuclear fuel cycles. At present, the development of effective actinide separation ligands has become a top priority. As common adsorbents for extracting uranium from seawater, amidoxime-based adsorbents may also be able to separate actinides from high-level liquid waste (HLLW). In this work, the complexation of Np(IV,V,VI) and Pu(IV) and alkyl chains (R = C13H26) modified with amidoximate (AO-) and carboxyl (Ac-) functional groups was systematically studied by quantum chemical calculations. For all the studied complexing species, the RAc- and RAO- ligands act as monodentate or bidentate ligands. Complexes with AO- groups show higher covalency of the metal-ligand bonding than the analogues with Ac- groups, in line with the binding energy analysis. Bonding analysis verifies that these amidoxime/carboxyl-based adsorbents possess higher coordination affinity toward Pu(IV) than toward Np(IV), and the Np(VI) complexes have stronger covalent interactions than Np(V). According to thermodynamic analysis, these adsorbents have the ability to separate Np(IV,V,VI) and Pu(IV), and also exhibit potential performance for partitioning Pu(IV) from Np(IV) under acidic conditions. This work can help to deeply understand the interaction between transuranium elements and amidoxime-based adsorbents, and provide a theoretical basis for the separation of actinides with amidoxime-based adsorbents.