Separation of lithium isotopes by N4S2 azacrown ion exchanger

Kim, D. W.; Kim, C. S.; Jeon, Jieun; Kim, J. S.; Lee, N. S.

doi:10.1007/bf02347479

Cited by 4 publications

(2 citation statements)

References 14 publications

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“…Similar fractionation factors were also estimated from natural studies of lithium in seafloor basalt, Fe-Mn crusts and Fe-oxyhydroxides (Chan et al, 1992; Chan and Hein, 2007;Wimpenny et al, 2010b) and experimental studies determining the fractionation of lithium during uptake into gibbsite, kaolinite, vermiculite, illite and smectite (Brenot et al, 2008;Zhang et al, 1998;Pistiner and Henderson, 2003; Williams and Hervig, 2005). The fractionation factor (a solid-solution ) depends on both mineral type and temperature (Brenot et al, 2008;Taylor and Urey, Kim et al (1991) Monobenzo-15-crown-5 5% H 2 O in acetonitrile 0.947 6 Li 23 Kim et al (1995) Dibenzo pyridino diamide azacrown (DBPDA) Acetonitrile 0.966 6 Li 20 Kim et al (1997) Cyclic triazatetramerrifield resin 1 M NH 4 Cl 0.932 6 Li 20 Kim et al (1998) Azacrown tetramerrifield peptide resin 0.5 M NH 4 Cl 1.00127 7 Li 25 Kim et al (1998) NTOE 0.01 M HCl 1.0242 7 Li 25 Kim et al (1999) N 4 O 2 azacrown 0.01 M NH 4 Cl 1.038 Unclear 20 Kim et al (2000) Amino benzo-15-crown-5 1 M NH 4 Cl 1.026 7 Li 20 Nishizawa and Watanabe (1986) Cryptand (2B,2,1) 0.959 6 Li Room temp. Nishizawa et al (1984) Benzo-15-crown-5 0.965-0.998 6 Li Room temp.…”

Section: Studies Of Lithium-isotope Fractionationmentioning

confidence: 99%

Lithium isotope fractionation during uptake by gibbsite

Wimpenny

Colla

Yu³

et al. 2015

Geochimica et Cosmochimica Acta

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The intercalation of lithium from solution into the six-membered l 2 -oxo rings on the basal planes of gibbsite is well-constrained chemically. The product is a lithiated layered-double hydroxide solid that forms via in situ phase change. The reaction has well established kinetics and is associated with a distinct swelling of the gibbsite as counter ions enter the interlayer to balance the charge of lithiation. Lithium reacts to fill a fixed and well identifiable crystallographic site and has no solvation waters. Our lithium-isotope data shows that 6 Li is favored during this intercalation and that the solid-solution fractionation depends on temperature, electrolyte concentration and counter ion identity (whether Cl À , NO 3 À or ClO 4 À ). We find that the amount of isotopic fractionation between solid and solution (DLi solid-solution ) varies with the amount of lithium taken up into the gibbsite structure, which itself depends upon the extent of conversion and also varies with electrolyte concentration and in the counter ion in the order: ClO 4 À < NO 3 À < Cl À . Higher electrolyte concentrations cause more rapid expansion of the gibbsite interlayer and some counter ions, such as Cl À , are more easily taken up than others, probably because they ease diffusion. The relationship between lithium loading and DLi solid-solution indicates two stages:(1) uptake into the crystallographic sites that favors light lithium, in parallel with adsorption of solvated cations, and (2) continued uptake of solvated cations after all available octahedral vacancies are filled; this second stage has no isotopic preference. The two-step reaction progress is supported by solid-state NMR spectra that clearly resolve a second reservoir of lithium in addition to the expected layered double-hydroxide phase.

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Section: Studies Of Lithium-isotope Fractionationmentioning

confidence: 99%

Lithium isotope fractionation during uptake by gibbsite

Wimpenny

Colla

Yu³

et al. 2015

Geochimica et Cosmochimica Acta

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“…10,11 Kim and co-workers developed a series of Merrifield peptide resins functionalized with various ligands including NTOE, N3O2, N4O2, N4S2, etc., and studied their separation performance on lithium isotopes in column chromatography. [12][13][14][15][16][17][18] Besides, chromatographic separation of lithium isotopes was also reported by researchers in Fujii's group, which impregnated or chemically-attached B15C5 to porous silica resins, resulting in a separation factor of 1.033 in methanol-hydrochloric acid mixed solution. 19,20 Recently, considerable attention was paid to the use of ionic liquids (ILs) as extractants or synergistic agents for separating lithium isotopes in liquid-liquid extraction, adsorption or membrane systems.…”

Section: Introductionmentioning

confidence: 98%

Macrocyclic ligand decorated ordered mesoporous silica with large-pore and short-channel characteristics for effective separation of lithium isotopes: synthesis, adsorptive behavior study and DFT modeling

Liu

et al. 2016

Dalton Trans.

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Effective separation of lithium isotopes is of strategic value which attracts growing attention worldwide. This study reports a new class of macrocyclic ligand decorated ordered mesoporous silica (OMS) with large-pore and short-channel characteristics, which holds the potential to effectively separate lithium isotopes in aqueous solutions. Initially, a series of benzo-15-crown-5 (B15C5) derivatives containing different electron-donating or -withdrawing substituents were synthesized. Extractive separation of lithium isotopes in a liquid-liquid system was comparatively studied, highlighting the effect of the substituent, solvent, counter anion and temperature. The optimal NH-B15C5 ligands were then covalently anchored to a short-channel SBA-15 OMS precursor bearing alkyl halides via a post-modification protocol. Adsorptive separation of the lithium isotopes was fully investigated, combined with kinetics and thermodynamics analysis, and simulation by using classic adsorption isotherm models. The NH-B15C5 ligand functionalized OMSs exhibited selectivity to lithium ions against other alkali metal ions including K(i). Additionally, a more efficient separation of lithium isotopes could be obtained at a lower temperature in systems with softer counter anions and solvents with a lower dielectric constant. The highest value separation factor (α = 1.049 ± 0.002) was obtained in CFCOOLi aqueous solution at 288.15 K. Moreover, theoretical computation based on the density functional theory (DFT) was performed to elucidate the complexation interactions between the macrocyclic ligands and lithium ions. A suggested mechanism involving an isotopic exchange equilibrium was proposed to describe the lithium isotope separation by the functionalized OMSs.

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