Abstract
We theoretically investigated the selective back-extraction towards Am(III) over Eu(III) and Cm(III) with two water-soluble 2,9-bis-triazolyl-1,10-phenanthroline derivatives BTrzPhen1 (with two ethanol side chains) and BTrz-Phen2 (with two 1,2-butanediol side chains) by density functional theory (DFT). The molecular geometries and formation reactions of the metal-ligand complexes were modeled by using M(BTrzPhen)(NO3)3 and [M(BTrzPhen)2(NO3)]2+. Am(III) selectivity over Eu(III) and Cm(III) with BTrzPhen2 was successfully reproduced by back-extraction reaction free energy analysis. Moreover, bonding properties between the metal cations and coordinated ligands (model complexes) were studied in terms of Mayer bond order and quantum theory of atoms in molecule (QTAIM). The difference in covalency between An–N and Eu–N bonds were found to be the key factors for Am(III)/Eu(III) separation, while the Am(III) selectivity over Cm(III) of BTrzPhen2 might be attributed to the competition of donor atoms for cation binding preference toward Am(III) and Cm(III).
Funding source: National Natural Science Foundation of China
Award Identifier / Grant number: 21906152
Award Identifier / Grant number: 21876174
Award Identifier / Grant number: 11875058
Award Identifier / Grant number: 11575212
Funding statement: This study was supported by the National Natural Science Foundation of China (Grant Nos. 21906152, 21876174, 11875058, 11575212), Major Program of National Natural Science Foundation of China (21790373), the Science Challenge Project (TZ2016004) and China Postdoctoral Science Foundation (Grant No. 2017M610995). This work is also funded by the Scientific Research Fund of Zhejiang Provincial Education department (Y201738897). The results described in this study were obtained on the ScGrid of the Supercomputing Center, Computer Network Information Center of Chinese Academy of Sciences.
Notes: The authors declare no competing financial interest.
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