Hemispherand-Strapped Calix[4]pyrrole: An Ion-pair Receptor for the Recognition and Extraction of Lithium Nitrite

He, Qing; Zhang, Zhan; Brewster, James T.; Lynch, Vincent M.; Kim, Sung Kuk; Sessler, Jonathan L.

doi:10.1021/jacs.6b05713

Cited by 102 publications

(78 citation statements)

References 31 publications

(15 reference statements)

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“…Further support for the fact that 2 and 3 are capable of capturing LiCl came from single crystal X-ray diffraction analyses.Suitable crystals of the LiCl complexes of 2 (2·LiCl) and 3 (3·LiCl) were obtained by subjecting aCH 2 Cl 2 /CH 3 OH/ CH 3 CN solution of 2 or aC H 3 CN/CH 3 OH solution of receptor 3 to slow evaporation in the presence of excess LiCl, respectively.Incontrast to what was seen in the case of 1·LiCl, in which awater molecule was observed to bridge the Li + cation and the Cl À anion, [11] receptors 2 and 3,a s anticipated, entrap the LiCl ion pair directly within their cavities.T his gives rise to close Li + ···Cl À distances of 2.67 and 2.38 ,respectively ( Figure 2). In the case of 2·LiCl, both the Li + and Cl À ions were found entirely embedded within the cavity of receptor 2,while in the case of 3·LiCl, the cation was forced to extrude from the cavity leading to distortion of the receptor framework.…”

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confidence: 76%

“…[7] Theu se of ion-pair receptors, [8] small molecules that are capable of binding anions and cations concurrently,m ay obviate this need. [11] However,neither our system nor Smithsp roved effective for LiCl under LLE conditions.T his failure may reflect an inability to stabilize LiCl complexes that are free of ab ridging water molecule between the co-bound charge dense Cl À and Li + .W e envisioned that the effectiveness and selectivity of ion-pair binding might be enhanced if direct contact between cobound ions could be enforced by the use of receptors containing smaller internal cavities since it might maximize the Coulombic attraction within the complex. In 2004, Smith and co-workers reported the SLE of LiCl (s) into CDCl 3 with selectivity ratios of 94:4:2 (LiCl/ NaCl/KCl) by means of aditopic ion-pair receptor.…”

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confidence: 78%

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Selective Solid–Liquid and Liquid–Liquid Extraction of Lithium Chloride Using Strapped Calix[4]pyrroles

Williams

et al. 2018

Angew Chem Int Ed

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LiCl is a classic "hard" ion salt that is present in lithium-rich brines and a key component in end-of-life materials (that is, used lithium-ion batteries). Its isolation and purification from like salts is a recognized challenge with potential strategic and economic implications. Herein, we describe two ditopic calix[4]pyrrole-based ion-pair receptors (2 and 3), that are capable of selectively capturing LiCl. Under solid-liquid extraction conditions, using 2 as the extractant, LiCl could be separated from a NaCl/KCl salt mixture containing as little as 1 % LiCl with circa 100 % selectivity, while receptor 3 achieved similar separations when the LiCl level was as low as 200 ppm. Under liquid-liquid extraction conditions using nitrobenzene as the non-aqueous phase, the extraction preference displayed by 2 is KCl>NaCl>LiCl. In contrast, 3 exhibits high selectivity towards LiCl over NaCl and KCl, with no appreciable extraction being observed for the latter two salts.

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confidence: 76%

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confidence: 78%

Selective Solid–Liquid and Liquid–Liquid Extraction of Lithium Chloride Using Strapped Calix[4]pyrroles

Williams

et al. 2018

Angew Chem Int Ed

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“…With the gradual exhaustion of land mineral resources, oceans and salt lakes have attracted world attention because they are abundant in inorganic mineral resources including Lithium (Li) and rubidium (Rb) . The high commercial values of Li as well as Rb result in explosive demand of them . However, the extraction of Li(I) and Rb(I) is faced with so many problems because of their unique physical and chemical properties .…”

Section: Introductionmentioning

confidence: 99%

“…[21][22][23][24][25] The high commercial values of Li as well as Rb result in explosive demand of them. [25][26][27] However, the extraction of Li(I) and Rb(I) is faced with so many problems because of their unique physical and chemical properties. [28,29] Therefore, the efficient extraction of Li(I) and Rb(I) is of urgent task from an environmental perspective and a commercial perspective.…”

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confidence: 99%

Simultaneous adsorption of Li(I) and Rb(I) by dual crown ethers modified magnetic ion imprinting polymers

et al. 2019

Applied Organom Chemis

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With the gradual exhaustion of land mineral resources, oceans and lakes have attracted world attention because they are abundant in inorganic mineral resources including lithium, potassium, rubidium and cesium. Lithium is becoming the key material in manufacturing of primary and secondary batteries used in various portable devices and hybrid/electric vehicles. Rubidium has been widely applied inglobal positioning satellites, magneto‐optic modulators, solid‐state lasers, phosphors, and glass manufacturing. In this work, a novel dual‐functional magnetic ion imprinting polymer (Fe3O4@SiO2@IIPs) powder was prepared using 12‐crown‐4 (12C4) and 18‐crown‐6 (18C6) as functional monomer, and characterized by FT‐IR, elemental analysis, XRD, TGA, SEM and TEM. The adsorption performance of Fe3O4@SiO2@IIPs for simultaneous adsorption of lithium and rubidium from simulative salt lakes was evaluated by batches of experiments at various pH values, contact time, and initial concentrations. Kinetic experiments show that the adsorption process followed the pseudo second order kinetic model. Langmuir adsorption isotherm model and Freundlich adsorption equilibrium data were fitted; the results show that Langmuir isotherm model is more suitable for the adsorption process. Additionally, Fe3O4@SiO2@IIPs exhibit specificity towards Li(I) and Rb(I) and low competitive behavior with Na(I), K(I) and Mg (II). Additionally, the selectivity properties, reusability and adsorption thermodynamic were also investigated. The obtained results show that the prepared Fe3O4@SiO2@IIPs material remains high adsorption capacities after five cycles, exhibits excellent abilities to simultaneously and selectively recover Li+ and Rb+ and have a promising application in the simultaneous adsorption of lithium and rubidium ions.

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“…29−31 In liquid−liquid systems, the extractants or ligands can be dissolved into one of the liquid phase while the analytes are present in the other phase. 32 The dissolution of the ion exchanger together with the extractants/ligands was shown to enhance the extraction efficiency and gave a reduced extraction time. 26 To the best of our knowledge, two-phase extraction systems based on the ion exchange principle have never been applied as titration reagents in complexometric titrations.…”

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confidence: 99%

Ionophore-Based Titrimetric Detection of Alkali Metal Ions in Serum

et al. 2017

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While the titrimetric assay is one of the most precise analytical techniques available, only a limited list of complexometric chelators is available, as many otherwise promising reagents are not water-soluble. Recent work demonstrated successful titrimetry with ion-exchanging polymeric nanospheres containing hydrophobic complexing agents, socalled ionophores, opening an exciting avenue in this field. However, this method was limited to ionophores of very high affinity to the analyte and exhibited a relatively limited titration capacity. To overcome these two limitations, we report here on solvent based titration reagents. This heterogeneous titration principle is based on the dissolution of all hydrophobic recognition components in a solvent such as dichloromethane (CH 2 Cl 2 ) where the ionophores are shown to maintain a high affinity to the target ions. HSV (hue, saturation, value) analysis of the images captured with a digital camera provides a convenient and inexpensive way to determine the end point. This approach is combined with an automated titration setup. The titrations of the alkali metals K + , Na + , and Li + in aqueous solution are successfully demonstrated. The potassium concentration in human serum without pretreatment was precisely and accurately determined as 4.38 mM ± 0.10 mM (automated titration), which compares favorably with atomic emission spectroscopy (4.47 mM ± 0.20 mM).

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Hemispherand-Strapped Calix[4]pyrrole: An Ion-pair Receptor for the Recognition and Extraction of Lithium Nitrite

Cited by 102 publications

References 31 publications

Selective Solid–Liquid and Liquid–Liquid Extraction of Lithium Chloride Using Strapped Calix[4]pyrroles

Selective Solid–Liquid and Liquid–Liquid Extraction of Lithium Chloride Using Strapped Calix[4]pyrroles

Simultaneous adsorption of Li(I) and Rb(I) by dual crown ethers modified magnetic ion imprinting polymers

Ionophore-Based Titrimetric Detection of Alkali Metal Ions in Serum

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