Quantum chemical studies of selective back-extraction of Am(III) from Eu(III) and Cm(III) with two hydrophilic 1,10-phenanthroline-2,9-bis-triazolyl ligands

Pin-Wen Huang 1 , Cong-Zhi Wang 2 , Qun-Yan Wu 2 , Jian-Hui Lan 2 , Zhi-Fang Chai 2 , 3 ,  and Wei-Qun Shi 2
  • 1 Zhejiang University of Water Resources and Electric Power, Hangzhou, Zhejiang 310018, China
  • 2 Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
  • 3 Engineering Laboratory of Advanced Energy Materials, Ningbo Institute of Industrial Technology, Chinese Academy of Sciences, Ningbo, Zhejiang 315201, China
Pin-Wen Huang
  • Zhejiang University of Water Resources and Electric Power, Hangzhou, Zhejiang 310018, China
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, Cong-Zhi Wang
  • Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
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, Qun-Yan Wu
  • Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
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, Jian-Hui Lan
  • Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
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, Zhi-Fang Chai
  • Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
  • Engineering Laboratory of Advanced Energy Materials, Ningbo Institute of Industrial Technology, Chinese Academy of Sciences, Ningbo, Zhejiang 315201, China
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and Wei-Qun Shi
  • Corresponding author
  • Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
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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).

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