Structural mechanism of selective binding of lithium on a solid matrix of Al(OH)3 from aqueous solutions

Исупов, В. П.; Габуда, С. П.; Kozlova, S. G.; Chupakhina, L. E.

doi:10.1007/bf02873642

Cited by 16 publications

(11 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The changes affecting the interatomic distances within the hydroxide layers are negligible. 16 Fig. 2 is a plot of the powder XRD of a-Al(OH) 3 (gibbsite), Li,Al-Cl and the product of de-intercalation of LiCl.…”

Section: Resultsmentioning

confidence: 99%

“…[11][12][13] Crystallographic studies have shown that upon intercalation, Li 1 ions occupy the remaining third of the octahedral sites within the structure of Al(OH) 3 giving [LiAl 2 (OH) 6 ] 1 layers, while the charge balancing anions X n2 and solvent molecules are accommodated between these layers. [14][15][16] This ordered arrangement results in some remarkable anion-exchange properties. 3,[17][18][19][20] However, a suspension of [LiAl 2 (OH) 6 ] n X?qH 2 O (X n2 ~Cl 2 , NO 3 2 , SO 4 22 ) in water is unstable and is accompanied by the partial release of both the Li 1 cations and the X n2 anions into solution.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

A time resolved, in-situ X-ray diffraction study of the de-intercalation of anions and lithium cations from [LiAl₂(OH)₆]_nX·qH₂O (X = Cl⁻, Br⁻, NO₃⁻, SO₄²⁻)

et al. 2004

View full text Add to dashboard Cite

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A time resolved, in-situ X-ray diffraction study of the de-intercalation of anions and lithium cations from [LiAl₂(OH)₆]_nX·qH₂O (X = Cl⁻, Br⁻, NO₃⁻, SO₄²⁻)

et al. 2004

View full text Add to dashboard Cite

“…In order to maintain charge balance, there is a vacancy in the six-membered ring and it is in this site that Li(I) reacts preferentially. The tendency for gibbsite to take up Li(I) in the rings is well known (Besserguenev et al, 1997;Isupov et al, 1998;Fogg and O'Hare, 1999;Wang et al, 2007) and is exploited industrially to form the layered-double-hydroxide solid [LiAl 2 (OH) 6 ]X.nH 2 O as written in Eq. (1), where X can be Cl,I,Br,or NO 3 :…”

Section: Intercalation In Gibbsitementioning

confidence: 98%

“…the six membered ring in the octahedral sheet). More detailed description of the Li(I)-intercalation mechanism is given in Isupov et al, 1998, andO'Hare, 2006. While the structure of gibbsite is well known and intercalation of Li(I) has been well studied (Besserguenev et al, 1997;Isupov et al, 1998;Fogg and O'Hare, 1999;Hou and Kirkpatrick, 2001), measurements of isotopic fractionation between solution and gibbsite is not. To date, only one previous study has investigated lithium-isotope fractionation during uptake into gibbsite (Pistiner and Henderson, 2003) showing that gibbsite preferentially takes up 6 Li from solution with a fractionation factor a solid-solution of 0.986.…”

Section: Intercalation In Gibbsitementioning

confidence: 99%

Lithium isotope fractionation during uptake by gibbsite

Wimpenny

Colla

Yu³

et al. 2015

Geochimica et Cosmochimica Acta

View full text Add to dashboard Cite

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.

show abstract

“…In gibbsite (Figure A and B), layers of edge-sharing Al 3+ (OH) 6 octahedra bound to each other through hydrogen bonding stack into a pseudohexagonal structure . Within each layer, only two-thirds of the octahedral cavities created by close-packed oxygen layers are occupied by Al 3+ ; the remaining unoccupied cavities have a radius of approximately 0.7 Å, enabling insertion of Li + , which has a radius of 0.68 Å . To balance the charge, Li + insertion occurs concurrently with incorporation of anions such as OH – , NO 3 – , Cl – , or CO 3 2– into the interlayer, as shown in Figure C,D.…”

Section: Introductionmentioning

confidence: 99%

Unraveling Gibbsite Transformation Pathways into LiAl-LDH in Concentrated Lithium Hydroxide

Graham

Zhang

et al. 2019

Inorg. Chem.

View full text Add to dashboard Cite

Gibbsite (α-Al(OH) 3 ) transformation into layered double hydroxides, such as lithium aluminum hydroxide dihydrate (LiAl-LDH), is generally thought to occur by solidstate intercalation of Li + , in part because of the intrinsic structural similarities in the quasi-2D octahedral Al 3+ frameworks of these two materials. However, in caustic environments where gibbsite solubility is high relative to LiAl-LDH, a dissolutionreprecipitation pathway is conceptually enabled, proceeding via precipitation of tetrahedral (T d ) aluminate anions (Al(OH) 4 − ) at concentrations held below 150 mM by rapid LiAl-LDH nucleation and growth. In this case, the relative importance of solid-state versus solution pathways is unknown because it requires in situ techniques that can distinguish Al 3+ in solution and in the solid phase (gibbsite and LiAl-LDH), simultaneously. Here, we examine this transformation in partially deuterated LiOH solutions, using multinuclear, magic angle spinning, and high field nuclear magnetic resonance spectroscopy ( 27 Al and 6 Li MAS NMR), with supporting X-ray diffraction and scanning electron microscopy. In situ 27 Al MAS NMR captured the emergence and decline of metastable aluminate ions, consistent with dissolution of gibbsite and formation of LiAl-LDH by precipitation. High field, ex situ 6 Li NMR of the the progressively reacted solids resolved an O h Li + resonance that narrowed during the transformation. This is likely due to increasing local order in LiAl-LDH, correlating well with observations in high field, ex situ 27 Al MAS NMR spectra, where a comparatively narrow LiAl-LDH O h 27 Al resonance emerges upfield of gibbsite resonances. No intermediate pentahedral Al 3+ is resolvable. Quantification of aluminate ion concentrations suggests a prominent role for the solution pathway in this system, a finding that could help improve strategies for manipulating Al 3+ concentrations in complex caustic waste streams, such as those being proposed to treat the high-level nuclear waste stored at the U.S. Department of Energy's Hanford Nuclear Reservation in Washington State, USA.

show abstract

Structural mechanism of selective binding of lithium on a solid matrix of Al(OH)3 from aqueous solutions

Cited by 16 publications

References 3 publications

A time resolved, in-situ X-ray diffraction study of the de-intercalation of anions and lithium cations from [LiAl₂(OH)₆]_nX·qH₂O (X = Cl⁻, Br⁻, NO₃⁻, SO₄²⁻)

A time resolved, in-situ X-ray diffraction study of the de-intercalation of anions and lithium cations from [LiAl₂(OH)₆]_nX·qH₂O (X = Cl⁻, Br⁻, NO₃⁻, SO₄²⁻)

Lithium isotope fractionation during uptake by gibbsite

Unraveling Gibbsite Transformation Pathways into LiAl-LDH in Concentrated Lithium Hydroxide

Contact Info

Product

Resources

About

Structural mechanism of selective binding of lithium on a solid matrix of Al(OH)3 from aqueous solutions

Cited by 16 publications

References 3 publications

A time resolved, in-situ X-ray diffraction study of the de-intercalation of anions and lithium cations from [LiAl2(OH)6]nX·qH2O (X = Cl−, Br−, NO3−, SO42−)

A time resolved, in-situ X-ray diffraction study of the de-intercalation of anions and lithium cations from [LiAl2(OH)6]nX·qH2O (X = Cl−, Br−, NO3−, SO42−)

Lithium isotope fractionation during uptake by gibbsite

Unraveling Gibbsite Transformation Pathways into LiAl-LDH in Concentrated Lithium Hydroxide

Contact Info

Product

Resources

About

A time resolved, in-situ X-ray diffraction study of the de-intercalation of anions and lithium cations from [LiAl₂(OH)₆]_nX·qH₂O (X = Cl⁻, Br⁻, NO₃⁻, SO₄²⁻)

A time resolved, in-situ X-ray diffraction study of the de-intercalation of anions and lithium cations from [LiAl₂(OH)₆]_nX·qH₂O (X = Cl⁻, Br⁻, NO₃⁻, SO₄²⁻)