Lipophilic phenanthroline diamide ligands in 1-octanol for separation of Am(III) from Eu(III)

Yang, Xiaofan; Liu, Yang; Tao, Wenjie; Wang, Shuai; Ren, Peng; Yang, Suliang; Yuan, Liyong; Tang, Hongliang; Chai, Zhifang; Shi, Wenjing

doi:10.1016/j.jece.2022.108401

Cited by 13 publications

(6 citation statements)

References 74 publications

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“…Among N-,O-donor ligands, phenanthroline and bipyridine ligands have been proposed as promising candidates to provide extraction features [19][20][21] and well-defined structure-property relationships. [22][23][24] However, applying a test-tube approach to compare extraction kinetics in systems with N-,O-donor ligands proves challenging due to the short times required to establish equilibrium.…”

Section: Introductionmentioning

confidence: 99%

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Kinetic features of solvent extraction by N,O-donor ligands of f-elements: a comparative study of diamides based on 1,10-phenanthroline and 2,2′-bipyridine

Konopkina,

Gopin,

Pozdeev

et al. 2024

Phys. Chem. Chem. Phys.

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Section: Introductionmentioning

confidence: 99%

“…Among N-,O-donor ligands, phenanthroline and bipyridine ligands have been proposed as promising candidates to provide extraction features 19–21 and well-defined structure–property relationships. 22–24…”

Section: Introductionmentioning

confidence: 99%

Kinetic features of solvent extraction by N,O-donor ligands of f-elements: a comparative study of diamides based on 1,10-phenanthroline and 2,2′-bipyridine

Konopkina,

Gopin,

Pozdeev

et al. 2024

Phys. Chem. Chem. Phys.

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“…The distribution of Am(III) by DAPhen ligands dissolved in n-octanol with the concentration of 10 mM is less than 1, which means the majority of Am(III) remains in aqueous phase. 23,27 Recently, various novel asymmetrical ligands have been developed for the extraction and complexation mechanism study of actinides and lanthanides based on combining the advantages of different functional groups. The ligand 6carboxylic di(2-ethylhexyl)amide pyridine (DEHAPA) (Figure 1b) contains a pyridine skeleton and other two functional groups, carboxylic acid and amide.…”

Section: ■ Introductionmentioning

confidence: 99%

Enhancing the Selectivity of Trivalent Actinide over Lanthanide Using Asymmetrical Phenanthroline Diamide Ligands

Wang,

Yang,

Liu

et al. 2024

Inorg. Chem.

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Phenanthroline diamide ligands have been widely used in the separation of trivalent actinides and lanthanides, but little research has focused on extractants with asymmetrical substitutes. Two novel asymmetrical phenanthroline-based ligands N 2,N 2,N 9-triethyl-N 9-tolyl-1,10-phenanthroline-2,9-dicarboxamide (DE-ET-DAPhen) and N 2-ethyl-N 9,N 9-dioctyl-N 2-tolyl-1,10-phenanthroline-2,9-dicarboxamide (DO-ET-DAPhen) were first synthesized in this work, whose extraction ability and complexation mechanism to trivalent actinides [An(III)] and lanthanides [Ln(III)] were systematically investigated. The ligands dissolved in n-octanol exhibit good extraction ability and high selectivity toward Am(III) in acidic solutions. The complexation mechanism of the ligands with Ln(III) in solution and solid state was analyzed using slope analysis, 1H NMR spectrometric titration, ESI-MS, and calorimetric titration. It is revealed that the ligands complex with Am(III)/Eu(III) with 1:1 stoichiometry. The stability constant (log β) of the complexation reaction of Eu(III) with DE-ET-DAPhen determined by UV–vis spectrophotometric and calorimetric titration is higher than that of DO-ET-DAPhen, indicating the stronger complexation ability of DE-ET-DAPhen. Meanwhile, the calorimetric titration results show that the complexation process is exothermic with a decreased entropy. The structures of 1:1 complexes of Eu(III) and Nd(III) with DE-ET-DAPhen were analyzed through single-crystal X-ray diffraction. This work proves that ligands containing asymmetrical functional groups are promising for An(III)/Ln(III) separation, which shows great significance in efficient extractants designed for the spent nuclear fuel reprocessing process.

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“…30,31 Therefore, some volatile and toxic solvents with greater polarity have been put to use for extraction of An(III). 32 The utilization of soft−hard hybrid N,O-ligands has also garnered great attention for the potential in the separation of An(III) and Ln(III). 33,34 Introduction of the softer N atom endowed the ligands with the better affinity to An(III) than Ln(III) through covalent interaction, while the harder O atom ensured the essential binding ability of ligands to metal ions.…”

Section: Introductionmentioning

confidence: 99%

“…Because of their extremely similar chemical behavior and ionic radius, separation of Ln(III)/An(III) has posed a major challenge in the field of nuclear industry. − As evidenced by a series of crystal structures and theoretical analyses of Ln(III)/An(III) complexes, some ligands involving N- or S-donors exhibited the greater affinity for An(III) than Ln(III) through covalent interactions. , Therefore, some typical soft ligands with N- or S-donors were widely developed for the selective complexation of An(III) from PUREX raffinate to reprocess minor actinides, such as the TRPO-Cyanex 301 process in China, the SANEX and GANEX processes in Europe, and the TRUEX and TALSPEAK strategies in the USA. ,, In these processes, some lipophilic or hydrophilic N-donor ligands were elaborately tailored including 2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl)pyridine, 6,6′-bis(5,6-dialkyl-1,2,4- triazin-3-yl)- 2,2′-bipyridine, and 2,9-bis(1,2,4-triazin-3-yl)-1,10-phenanthrolines, which exhibited excellent affinity toward MA elements. − Nevertheless, there are still certain limitations for these ligands in the separation of An(III), such as their limited solubility in nonpolar n -paraffin. , Therefore, some volatile and toxic solvents with greater polarity have been put to use for extraction of An(III) …”

Section: Introductionmentioning

confidence: 99%

Selective Separation of Americium(III), Curium(III), and Lanthanide(III) by Aqueous and Organic Competitive Extraction

Wu,

Hao,

Liu

et al. 2023

Inorg. Chem.

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Adding hydrophilic ligands into aqueous solutions for the selective binding of actinides(III) is acknowledged as an advanced strategy in Ln(III)/ An(III) separation. In view of the recycling and radioactive waste disposal of the minor actinide, there remains an urgent need to design and develop the appropriate ligand for selective separation of An(III) from Ln(III). Herein, four novel hydrophilic ligands with hard−soft hybrid donors, derived from the pyridine and phenanthroline skeletons, were designed and synthesized as masking agents for selective complexation of An(III) in the aqueous phase. The known N,N,N′,N′-tetraoctyl diglycolamide (TODGA) was used as lipophilic extractant in the organic phase for extraction of Ln(III), and a new strategy for the competitive extraction of An(III) and Ln(III) was developed based on TODGA and the above hydrophilic ligands. The optimal hydrophilic ligand of N,N′-bis(2hydroxyethyl)-2,9-dicarboxamide-1,10-phenanthroline (2OH-DAPhen) displayed exceptional selectivity toward Am(III) over Ln(III), with the concentrations of HNO 3 ranging from 0.05 to 3.0 M. The maximum separation factors were up to 1365 for Eu/Am, 417.66 for Eu/Cm, and 42.38 for La/Am. The coordination mode and bonding property of 2OH-DAPhen with Ln(III) were investigated by 1 H NMR titration, UV−vis spectrophotometric titration, luminescence titration, FT-IR, ESI-HRMS analysis, and DFT calculations. The results revealed that the predominant species formed in the aqueous phase was a 1:1 ligand/metal complex. DFT calculations also confirmed that the affinity of 2OH-DAPhen for Am(III) was better than that for Eu(III). The present work using a competitive extraction strategy developed a feasible alternative method for the selective separation of trivalent actinides from lanthanides.

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Lipophilic phenanthroline diamide ligands in 1-octanol for separation of Am(III) from Eu(III)

Cited by 13 publications

References 74 publications

Kinetic features of solvent extraction by N,O-donor ligands of f-elements: a comparative study of diamides based on 1,10-phenanthroline and 2,2′-bipyridine

Kinetic features of solvent extraction by N,O-donor ligands of f-elements: a comparative study of diamides based on 1,10-phenanthroline and 2,2′-bipyridine

Enhancing the Selectivity of Trivalent Actinide over Lanthanide Using Asymmetrical Phenanthroline Diamide Ligands

Selective Separation of Americium(III), Curium(III), and Lanthanide(III) by Aqueous and Organic Competitive Extraction

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