Excellent selectivity for actinides with a tetradentate 2,9-diamide-1,10-phenanthroline ligand in highly acidic solution: A hard-soft donor combined strategy

Cheng Liang Xiao, Cong Zhi Wang, Li Yong Yuan, Bin Li, Hui He, Shuao Wang, Yu Liang Zhao, Zhi Fang Chai, Wei Qun Shi

Research output: Contribution to journalArticle

112 Scopus citations

Abstract

In this work, we reported a phenanthroline-based tetradentate ligand with hard-soft donors combined in the same molecule, N,N′-diethyl-N,N′- ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen), for the group separation of actinides over lanthanides. The synthesis and solvent extraction as well as complexation behaviors of the ligand with actinides and lanthanides are studied experimentally and theoretically. The ligand exhibits excellent extraction ability and high selectivity toward hexavalent, tetravalent, and trivalent actinides over lanthanides in highly acidic solution. The chemical stoichiometry of Th(IV) and U(VI) complexes with Et-Tol-DAPhen is determined to be 1:1 using X-ray crystallography. The stability constants of some typical actinide and lanthanide complexes of Et-Tol-DAPhen are also determined in methanol by UV-vis spectrometry. Density functional theory (DFT) calculations reveal that the An-N bonds of the Et-Tol-DAPhen complexes have more covalent characters than the corresponding Eu-N bonds, which may in turn lead to the selectivity of Et-Tol-DAPhen toward actinides. This ligand possesses merits of both alkylamide and 2,9-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-1,10-phenanthroline (R-BTPhen) extractants for efficient actinide extraction and the selectivity toward minor actinides over lanthanides and hence renders huge potential opportunities in high-level liquid waste (HLLW) partitioning.

Original languageEnglish (US)
Pages (from-to)1712-1720
Number of pages9
JournalInorganic Chemistry
Volume53
Issue number3
DOIs
StatePublished - Feb 3 2014

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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