Insights from quantum chemical calculations ...
Document type :
Communication dans un congrès avec actes
Title :
Insights from quantum chemical calculations into inner and outer-sphere complexation of plutonium(IV) by monoamide and carbamide extractants
Author(s) :
Failali, Abdelmounaim [Orateur]
Laboratory of Interactions Ligand-Actinide [LILA]
Physico-Chimie Moléculaire Théorique [PCMT]
Guillaumont, Dominique [Auteur]
Laboratory of Interactions Ligand-Actinide [LILA]
Acher, Eléonor [Auteur]
Laboratory of Interactions Ligand-Actinide [LILA]
Vallet, Valérie [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Réal, Florent [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Laboratory of Interactions Ligand-Actinide [LILA]
Physico-Chimie Moléculaire Théorique [PCMT]
Guillaumont, Dominique [Auteur]
Laboratory of Interactions Ligand-Actinide [LILA]
Acher, Eléonor [Auteur]
Laboratory of Interactions Ligand-Actinide [LILA]
Vallet, Valérie [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Réal, Florent [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Conference title :
JdA-2021: 50èmes Journées des Actinides
City :
Rennes
Country :
France
Start date of the conference :
2021-03-22
Publication date :
2021-03-22
HAL domain(s) :
Chimie/Chimie théorique et/ou physique
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]
English abstract : [en]
In the context of nuclear fuel reprocessing, the recovery and purification of major actinides is achieved using a hydrometallurgical process known as PUREX (Plutonium Uranium Recovering by Extraction). Based on Liquid-Liquid ...
Show more >In the context of nuclear fuel reprocessing, the recovery and purification of major actinides is achieved using a hydrometallurgical process known as PUREX (Plutonium Uranium Recovering by Extraction). Based on Liquid-Liquid extraction technics, this process requires a specific molecule to extract Pu and U, the Tri-n-butyl phosphate TBP. Monoamides are regarded as alternative family of extraction molecules to TBP, as they are well known for their strong extraction ability of Pu(IV) and U(VI) elements. In addition to this, they show some interesting features, such as the complete incinerability of the solvent degradation products, and a strong dependence of the extraction properties (distribution coefficient and selectivity) on the chemical conditions [1-3]. <br><br>The strong influence of the structure of amide derivatives on their extraction properties has been demonstrated in several studies in the literature. In this study, we propose to investigate and rationalize the influence of the nature and length of the monoamide alkyl chains on Pu(IV) extraction/complexation, using the Density Functional Theory (DFT) method in the scalar relativistic framework. We will discuss the geometries of the inner/outer-sphere complexes and the interaction energies of [Pu(NO<sub>3</sub>)<sub>4</sub>] and [Pu(NO<sub>3</sub>)<sub>6</sub>]<sup>2-</sup> with different monoamide and carbamide ligands have been calculated. Our investigation focuses on discriminating the influence of the bulkiness of the alkyl group, and that of the solvent polarity on the stability of inner and outer-sphere complexes. This study suggests key possibilities to tune the substituent effect by changing the polarity of the solution [4]. <br><br>References<br>[1]G. Milanole et al. WO/2018/138441 (2018).<br>[2]C. Berger et al., Solvent Extr. Ion Exch., 37 , 111-125 (2019).<br>[3]E. Acher et al., Inorg. Chem., 55, 5558-5569 (2016). <br>[4]A. Failali et al., Phys. Chem. Chem. Phys., 23, 2229-2237 (2021).<br>Show less >
Show more >In the context of nuclear fuel reprocessing, the recovery and purification of major actinides is achieved using a hydrometallurgical process known as PUREX (Plutonium Uranium Recovering by Extraction). Based on Liquid-Liquid extraction technics, this process requires a specific molecule to extract Pu and U, the Tri-n-butyl phosphate TBP. Monoamides are regarded as alternative family of extraction molecules to TBP, as they are well known for their strong extraction ability of Pu(IV) and U(VI) elements. In addition to this, they show some interesting features, such as the complete incinerability of the solvent degradation products, and a strong dependence of the extraction properties (distribution coefficient and selectivity) on the chemical conditions [1-3]. <br><br>The strong influence of the structure of amide derivatives on their extraction properties has been demonstrated in several studies in the literature. In this study, we propose to investigate and rationalize the influence of the nature and length of the monoamide alkyl chains on Pu(IV) extraction/complexation, using the Density Functional Theory (DFT) method in the scalar relativistic framework. We will discuss the geometries of the inner/outer-sphere complexes and the interaction energies of [Pu(NO<sub>3</sub>)<sub>4</sub>] and [Pu(NO<sub>3</sub>)<sub>6</sub>]<sup>2-</sup> with different monoamide and carbamide ligands have been calculated. Our investigation focuses on discriminating the influence of the bulkiness of the alkyl group, and that of the solvent polarity on the stability of inner and outer-sphere complexes. This study suggests key possibilities to tune the substituent effect by changing the polarity of the solution [4]. <br><br>References<br>[1]G. Milanole et al. WO/2018/138441 (2018).<br>[2]C. Berger et al., Solvent Extr. Ion Exch., 37 , 111-125 (2019).<br>[3]E. Acher et al., Inorg. Chem., 55, 5558-5569 (2016). <br>[4]A. Failali et al., Phys. Chem. Chem. Phys., 23, 2229-2237 (2021).<br>Show less >
Language :
Anglais
Peer reviewed article :
Oui
Audience :
Internationale
Popular science :
Non
Source :