Extraction separation of lithium isotopes with Bromobenzene-15-crown-5/ionic liquids system: Experimental and theoretical study

Zhang, Pengrui; Wang, Ciming; Xue, Zixuan; Mao, Lianjing; Sun, Jinhe; Shao, Fei; Qi, Mixiang; Jing, Yan; Jia, Yongzhong

doi:10.1016/j.molliq.2022.120020

Cited by 10 publications

(6 citation statements)

References 48 publications

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“…The C 8 has demonstrated the most significant improvements in Li extraction ( D Li , 4.29 at 298 K; D Li , 7.59 at 273 K), which is nearly threefold higher than the extraction for B15C5 ( D Li , 1.54 at 298 K) under the same conditions. Moreover, it surpasses those previously reported CE or CE functional materials and [C n mim][NTf 2 ] systems with D Li around 10 –4 –0.09. − …”

Section: Resultsmentioning

confidence: 42%

Benzo-15-Crown-5 Functionalized Ionic Liquids with Enhanced Stability for Effective Separation of Lithium Isotopes: The Effect of Alkyl Chain Length

Cui,

Gao,

Zhang

et al. 2024

ACS Sustainable Chem. Eng.

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Crown ethers (CEs) are promising materials for lithium isotope ( 6 Li and 7 Li) separation for their unique cavity structure and size effect, but the low partitioning of Li + makes the practical implementation not applicable. The loss of CE molecules is also a critical problem. In this work, benzo-15-crown-5 functionalized imidazolium ionic liquids with different alkyl chain lengths ([C n (B15C5)mim][NTf 2 ], n = 6, 8, 10) are synthesized. The association constants of [C n (B15C5)mim][NTf 2 ] and Li + , Li + partition, and the separation factor of 6 Li and 7 Li using [C n (B15C5)mim][NTf 2 ] were investigated. Compared with the B15C5 monomer, the covalent bonding of B15C5 onto the cation of imidazolium ILs contributes to the dramatic increase of binding ability toward Li + . The association constants of [C n (B15C5)mim]-[NTf 2 ] with Li + increase with the elevation of the alkyl chain length due to the flexibility changes. However, [C 8 (B15C5)mim][NTf 2 ] delivers the most outstanding partition coefficient of Li + up to 7.59 with a separation factor of 1.033 (273 K), exceeding those reported for CE-based materials. The increased hydrophobicity of [C n (B15C5)mim][NTf 2 ] enables sustainable and robust use in the separation process. Both molecular dynamics simulations and interfacial tension experiments confirm that [C 8 (B15C5)mim][NTf 2 ] exhibits the best affinity to the interfaces of dichloroethane/water. The coordination environment of Li + can be tuned by regulating the length of the alkyl chains, resulting in different isotopic effects. This study offers a promising system for the effective and sustainable separation of 6 Li and 7 Li.

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Section: Resultsmentioning

confidence: 42%

Benzo-15-Crown-5 Functionalized Ionic Liquids with Enhanced Stability for Effective Separation of Lithium Isotopes: The Effect of Alkyl Chain Length

Cui,

Gao,

Zhang

et al. 2024

ACS Sustainable Chem. Eng.

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“…Therefore, the stronger the hydrophilicity of the cations of the ionic liquid, the easier it is to exchange with lithium ions in the aqueous phase and the higher the extraction rate. 35 With the growth of the carbon chain, the hydrophilicity of cations decreases while the viscosity increases, thereby inhibiting the exchange of cations in the organic phase and lithium ions in the aqueous phase. 36–38 However, the above discussions related to exchange kinetics have difficulty fully explaining the phenomenon that the extraction rate still shows a downward trend after extraction equilibrium.…”

Section: Resultsmentioning

confidence: 99%

The extraction method for the separation of lithium isotopes using B12C4/B15C5/B18C6-ionic liquid systems

Zhou

Zhang

Meng³

et al. 2023

New J. Chem.

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“…In the supramolecular chemistry field, reported extractants normally include cation-binding receptors and ion-pair receptors [ 11 ]. A pioneering lithium binding receptor was reported in the 1980s, displaying selective lithium extraction using spherand macrocycles [ 12 , 13 ], followed by many crown ether macrocycles and cryptand-based receptors [ 14 , 15 , 16 ]. These systems typically rely on an ion exchange process or are suitable for use in the presence of lipophilic countercations (e.g., picrate and perchlorate) for the extraction process [ 17 ].…”

Section: Introductionmentioning

confidence: 99%

Selective Solid–Liquid Extraction of Lithium Cation Using Tripodal Sulfate-Binding Receptors Driven by Electrostatic Interactions

Chen,

He,

Yan

et al. 2024

Molecules

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Owing to the important role of and increasing demand for lithium resources, lithium extraction is crucial. The use of molecular extractants is a promising strategy for selective lithium recovery, in which the interaction between lithium and the designed extractant can be manipulated at the molecular level. Herein, we demonstrate that anion receptors of tripodal hexaureas can selectively extract Li2SO4 solids into water containing DMSO (0.8% water) compared to other alkali metal sulfates. The hexaurea receptor with terminal hexyl chains displays the best Li+ extraction selectivity at 2-fold over Na+ and 12.5-fold over K+. The driving force underpinning selective lithium extraction is due to the combined interactions of Li+-SO42− electrostatics and the ion–dipole interaction of the lithium–receptor (carbonyl groups and N atoms); the latter was found to be cation size dependent, as supported by computational calculations. This work indicates that anion binding receptors could drive selective cation extraction, thus providing new insights into the design of receptors for ion recognition and separation.

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Extraction separation of lithium isotopes with Bromobenzene-15-crown-5/ionic liquids system: Experimental and theoretical study

Cited by 10 publications

References 48 publications

Benzo-15-Crown-5 Functionalized Ionic Liquids with Enhanced Stability for Effective Separation of Lithium Isotopes: The Effect of Alkyl Chain Length

Benzo-15-Crown-5 Functionalized Ionic Liquids with Enhanced Stability for Effective Separation of Lithium Isotopes: The Effect of Alkyl Chain Length

The extraction method for the separation of lithium isotopes using B12C4/B15C5/B18C6-ionic liquid systems

Selective Solid–Liquid Extraction of Lithium Cation Using Tripodal Sulfate-Binding Receptors Driven by Electrostatic Interactions

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