Highly efficient actinide(III)/lanthanide(III) separation by novel pillar[5]arene-based picolinamide ligands: A study on synthesis, solvent extraction and complexation

Cai, Yimin; Ansari, Seraj A.; Fu, Kuirong; Zhu, Bi‐Xue; Ma, Haoyang; Chen, Lixi; Conradson, Steven D.; Qin, Song; Fu, Haiying; Mohapatra, P. Κ.; Yuan, Lihua; Feng, Wen

doi:10.1016/j.jhazmat.2020.124214

Cited by 25 publications

(19 citation statements)

References 67 publications

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“…Whereas the D value largely decreased with L II after substitution of the electron-withdrawing chlorine group, the D value significantly enhanced after substitution of the electron-donating methoxy group in L III . This extraction pattern is completely opposite when the distribution studies were performed in the molecular solvent (70% NPOE +30% DCE) . In molecular solvents, the D value for Am 3+ and Eu 3+ was higher with L II (after substitution of the electron-withdrawing chlorine group) and lower with L III (after substitution of the electron-donating methoxy group).…”

Section: Resultsmentioning

confidence: 86%

“…In the light of our previous work on these ligands for the extraction of Am 3+ and Eu 3+ in molecular solvent (70% NPOE +30% DCE), 15 a mixture solution of 0.2 mM L III + 0.4 mM Br-Cosan was prepared first in C 4 mim•Tf 2 N. Similar to the molecular solvent, the D M values for Am 3+ and Eu 3+ increased with the aqueous phase pH in the IL phase as well (Figure 3). However, the D M values were very high in the IL medium as compared to molecular diluent even when 10 times lower concentration of the ligand was employed.…”

Section: Effect Of Br-cosan On Extraction Of Metal Ionsmentioning

confidence: 99%

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Unassisted and Efficient Actinide/Lanthanide Separation with Pillar[5]arene-Based Picolinamide Ligands in Ionic Liquids

Cai

Ansari

Yuan

et al. 2023

Ind. Eng. Chem. Res.

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Actinide/lanthanide separation is crucial for the development of nuclear industries, while this is largely hindered by their similar chemical and physical properties. In this work, we report solvent extraction systems comprising different pillar[5]arene-based picolinamide ligands with various substituted groups and the ionic liquid, C 4 mimNTf 2 , for efficient actinide/lanthanide separation from acidic solutions. Changing the pyridine nitrogen basicity by substituting the chlorine group (−I effect) or methoxy group (+I effect) at the para-position changes the extraction performance of the ligands substantially. The chlorine group gave negative extraction performance while the methoxy group enhanced the metal ion extraction ability by three orders of magnitude. Extraction kinetics for Am 3+ and Eu 3+ was fast, and equilibrium distribution values were reached within 15 min with all three ligands. Slope analyses suggested that the stoichiometry of the extracted complexes of Am 3+ and Eu 3+ with the three ligands is M/L 2/1, and each metal ion is extracted following the cation exchange mechanism involving the transfer of three C 4 mim + cations into the aqueous phase. Fluorescence spectroscopic investigation indicated that the extracted complexes were much distorted and ligands were directly coordinated to the metal ion with no sign of water molecules in the primary coordination sphere. The possible complexation structures of the ligands and the Eu 3+ ion were optimized by density functional theory calculations, which confirmed that the differences in the extraction ability of the ligands originate from different bonding strength between pyridine nitrogens and metal ions.

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Section: Resultsmentioning

confidence: 86%

Section: Effect Of Br-cosan On Extraction Of Metal Ionsmentioning

confidence: 99%

Unassisted and Efficient Actinide/Lanthanide Separation with Pillar[5]arene-Based Picolinamide Ligands in Ionic Liquids

Cai

Ansari

Yuan

et al. 2023

Ind. Eng. Chem. Res.

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“…The absolute value of log K of L I is larger than that of L II , which means that Nd(III) is more prone to complexation with L I ligand than with L II ligand at 298 K. The negative values of DS is because the degree of disorder in the extraction systems is reduced by the formation of the extracted species. 57 The thermodynamic data on the extraction reaction combined with the results of the D Nd demonstrates that the L I ligand has better Nd(III) extraction capability.…”

Section: Solvent Extractionmentioning

confidence: 94%

A comparative study on the coordination of diglycolamide isomers with Nd(iii): extraction, third phase formation, structure, and computational studies

et al. 2021

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“…In addition, anchoring chelating groups to the framework of pillar[5]arenes can result in improved stability of metal complexes . Our previous research on pillar[5]arene-based extractants for actinide/lanthanide separation indicated significantly enhanced stability of the separating materials. , Interest in metal–salen complexes as homogeneous catalysts has risen with their ability to promote efficient CO 2 /epoxide coupling reactions under mild reaction conditions for cyclic organic carbonates . In some cases, these complexes exhibit higher reactivity for the synthesis of optically active cyclic carbonates .…”

Section: Introductionmentioning

confidence: 99%

Pillar[5]arene-Based Co(III)-Loaded Covalent Organic Polymer for Efficient CO₂ Cycloaddition under Mild Conditions

et al. 2022

ACS Sustainable Chem. Eng.

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Generating promising materials for the conversion of CO2 to valuable industrial products under mild conditions is important for both ameliorating the greenhouse effect and sustainable development. Pillar[5]arene-incorporated materials have recently emerged as building frameworks to construct versatile functional polymeric materials. Herein, we demonstrate that highly efficient fixation of CO2 to cyclic carbonates can be achieved by employing a novel pillar[5]arene-based Co(III)-loaded covalent organic polymer (COP) as a heterogeneous catalyst (Co(III)–P5COP). The catalyst was created first by condensation of bromo-functionalized pillar[5]arene and a Schiff-base derivative (BHPD–OH) to afford the pillar[5]arene-based COP (P5COP), followed by loading Co(III) to prepare the target material bearing abundant salen–Co(III) sites. Results of catalysis with various substrates reveal excellent catalytic performance for CO2 cycloaddition with the conversion and selectivity of cyclic carbonate reaching up to 96 and 99%, respectively, under mild conditions of 30 °C and 1 atm CO2. Moreover, Co(III)–P5COP exhibits general applicability to other bulky epoxides. The polymeric pillar[5]arene-based catalysts could be easily recovered and reused without marked loss in their activity. Therefore, the marriage of Co(III)–salen and the pillar[5]arene platform constitutes a feasible approach to offering easily accessible and macrocycle-based new materials for the conversion of CO2 to valuable products.

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Highly efficient actinide(III)/lanthanide(III) separation by novel pillar[5]arene-based picolinamide ligands: A study on synthesis, solvent extraction and complexation

Cited by 25 publications

References 67 publications

Unassisted and Efficient Actinide/Lanthanide Separation with Pillar[5]arene-Based Picolinamide Ligands in Ionic Liquids

Unassisted and Efficient Actinide/Lanthanide Separation with Pillar[5]arene-Based Picolinamide Ligands in Ionic Liquids

A comparative study on the coordination of diglycolamide isomers with Nd(iii): extraction, third phase formation, structure, and computational studies

Pillar[5]arene-Based Co(III)-Loaded Covalent Organic Polymer for Efficient CO₂ Cycloaddition under Mild Conditions

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Highly efficient actinide(III)/lanthanide(III) separation by novel pillar[5]arene-based picolinamide ligands: A study on synthesis, solvent extraction and complexation

Cited by 25 publications

References 67 publications

Unassisted and Efficient Actinide/Lanthanide Separation with Pillar[5]arene-Based Picolinamide Ligands in Ionic Liquids

Unassisted and Efficient Actinide/Lanthanide Separation with Pillar[5]arene-Based Picolinamide Ligands in Ionic Liquids

A comparative study on the coordination of diglycolamide isomers with Nd(iii): extraction, third phase formation, structure, and computational studies

Pillar[5]arene-Based Co(III)-Loaded Covalent Organic Polymer for Efficient CO2 Cycloaddition under Mild Conditions

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Product

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Pillar[5]arene-Based Co(III)-Loaded Covalent Organic Polymer for Efficient CO₂ Cycloaddition under Mild Conditions