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New insights into the selectivity of four 1,10-phenanthroline-derived ligands toward the separation of trivalent actinides and lanthanides: a DFT based comparison study
Wu H(吴晗); Wu QY(吴群燕); Wang CZ(王聪芝); Lan JH(蓝建慧); Chai ZF(柴之芳); Shi WQ(石伟群); Wu, H; Wu, QY; Wang, CZ; Lan, JH; Liu, ZR; Chai, ZF; Shi, WQ
2016
Source PublicationDALTON TRANSACTIONS
ISSN1477-9226
EISSN1477-9234
Volume45Issue:19Pages:8107-8117
SubtypeArticle
AbstractAlthough many heterocyclic N-donor ligands have shown excellent competence for separating actinides from lanthanides, an explanation for why some ligands work whereas others fail is very fundamental but greatly needs to be addressed for designing novel and efficient extractants. In this work, we systematically investigated four phenanthroline-derived ligands, DHDIPhen, BQPhen, Ph2-BTPhen and CyMe4-BTPhen, and their coordination geometrical properties and formation reactions with Am(III) and Eu(III) ions by quasi-relativistic density functional theory. The calculated hardness of ligands, which may help to determine their selectivity toward actinides and lanthanides, yielded an order, from the softest to the hardest, as follows: Ph2-BTPhen < CyMe4-BTPhen < BQPhen < DHDIPhen. It shows that the intramolecular hydrogen bonds and size of a ligand cavity are two dominant factors for metal-ion complexation. Natural population analysis (NPA) reveals that the 5d/6d orbitals of Eu/Am accept significantly more electrons than other orbitals, but partial density of states and molecular orbital analysis prove that the d orbitals with more accepted electrons have little contribution to the metal-ligand bonds. The thermodynamic results suggest that ligand protonation does have a great influence on the complexation of ligands with metal ions but does not change the selectivity of ligands toward metal ions. This work can help in-depth understanding the differences of selectivity of various structurally similar ligands and provide more theoretical insights for designing more innovative ligands for Ln/An separation.
DOI10.1039/c6dt00296j
Indexed BySCI
Language英语
WOS IDWOS:000375605900019
Citation statistics
Document Type期刊论文
Identifierhttp://ir.ihep.ac.cn/handle/311005/248025
Collection院士
多学科研究中心
Recommended Citation
GB/T 7714
Wu H,Wu QY,Wang CZ,et al. New insights into the selectivity of four 1,10-phenanthroline-derived ligands toward the separation of trivalent actinides and lanthanides: a DFT based comparison study[J]. DALTON TRANSACTIONS,2016,45(19):8107-8117.
APA 吴晗.,吴群燕.,王聪芝.,蓝建慧.,柴之芳.,...&Shi, WQ.(2016).New insights into the selectivity of four 1,10-phenanthroline-derived ligands toward the separation of trivalent actinides and lanthanides: a DFT based comparison study.DALTON TRANSACTIONS,45(19),8107-8117.
MLA 吴晗,et al."New insights into the selectivity of four 1,10-phenanthroline-derived ligands toward the separation of trivalent actinides and lanthanides: a DFT based comparison study".DALTON TRANSACTIONS 45.19(2016):8107-8117.
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