Issue 13, 2020

Theoretical insights into selective separation of trivalent actinide and lanthanide by ester and amide ligands based on phenanthroline skeleton

Abstract

Phenanthroline based ligands have shown potential performance for partitioning trivalent actinides from lanthanides. In this work, we have explored four ester and amide ligands based on the phenanthroline skeleton and elucidated the separation mechanism between Am(III) and Eu(III) ions. The molecular geometries and extraction reactions of the metal–ligand complexes were modeled by using scalar-relativistic density functional theory. The results show that the amide based ligands have stronger coordination ability with the metal ions than the corresponding ester based ligands. According to the thermodynamic results, ligands N,N′-diethyl-N,N′-ditolyl-2,9-diamide-1,10-phenanthroline (L2) and N,N′-(1,10-phenanthroline-2,9-diyl)bis(N-ethyl-P-methyl-N-(p-tolyl)phosphinic amide) (L4) appear to have the strongest complexing ability, which is supported by the result of electrostatic potential (ESP) and the M–OL bond orders. Moreover, ligand L2 has excellent selectivity for Am(III)/Eu(III) among the four ligands. Additionally, the bonding properties between the metal ions and the ligands reveal that the Am(III)/Eu(III) selectivity stems from the Am–N bonds with more covalent character, which is supported by the analysis of the hardness of the ligands and the bond orders. This work provides useful information for understanding the Am(III)/Eu(III) selectivity of phenanthroline derived ligands bearing ester and amide groups.

Graphical abstract: Theoretical insights into selective separation of trivalent actinide and lanthanide by ester and amide ligands based on phenanthroline skeleton

Supplementary files

Article information

Article type
Paper
Submitted
19 Jan 2020
Accepted
23 Feb 2020
First published
24 Feb 2020

Dalton Trans., 2020,49, 4093-4099

Theoretical insights into selective separation of trivalent actinide and lanthanide by ester and amide ligands based on phenanthroline skeleton

C. Wang, Q. Wu, C. Wang, J. Lan, C. Nie, Z. Chai and W. Shi, Dalton Trans., 2020, 49, 4093 DOI: 10.1039/D0DT00218F

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements