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Hydration, expansion, structure, and dynamics of layered double hydroxides

Xiaoqiang Hou, David L. Bish, Shan-Li Wang, Cliff T. Johnston and R. James Kirkpatrick
Hydration, expansion, structure, and dynamics of layered double hydroxides
American Mineralogist (January 2003) 88 (1): 167-179

Abstract

Water-vapor sorption isotherms, relative humidity (RH) controlled powder X-ray diffraction (XRD) data, and new and previously published multi-Nuclear NMR spectroscopic data for a wide range of layered double hydroxides (LDHs) provide greatly increased understanding of the effects of hydration state on the structure and dynamical behavior of interlayer and surface anions and the factors controlling the expansion behavior of this group of minerals. Li, Al and Mg,Al LDH phases containing SO (super 2-) (sub 4) , SeO (super 2-) (sub 4) , PO (super 3-) (sub 4) , HPO (super 2-) (sub 4) , MoO (super 2-) (sub 4) , ClO (super -) (sub 4) , SeO (super 2-) (sub 3) , CO (super 2-) (sub 3) , F (super -) , Cl (super -) , Br (super -) , I (super -) , OH (super -) , and NO (super -) (sub 3) were examined. The phases studied can be grouped into three types based on basal spacing expansion, water sorption, and interlayer anion dynamics: Type 1, significantly expandable (1.5-3.0 Aa); Type 2, slightly expandable (expansion >0.5 Aa) and with significant interlayer water exchange; and Type 3, essentially non-expandable (0-0.2 Aa) and with little interlayer water exchange. For Type 1, the fully expanded phases have a two-water layer structure, and the phase transition from one layer to two layers as determined by XRD consistently correlates with a significant step in the water sorption isotherm and with changes in the interlayer structure and dynamics as observed by NMR spectroscopy. For Type-2 phases, only one-water layer structures form, and the interlayer anions may undergo dynamical disordering with increasing RH, as observed by NMR. For both Types 1 and 2, the first water layer does not cause significant basal spacing expansion due to occupancy of vacant interstitial sites between the anions by the water molecules. For Type -3 phases, there is little interlayer water sorption because the interlayers are essentially closed due to the small size or planar shape of the anions and their strong electrostatic and hydrogen bonding interaction with hydroxyl layers. RH has no effect on the structural environments and dynamics of the interlayer anions in this group.


ISSN: 0003-004X
EISSN: 1945-3027
Coden: AMMIAY
Serial Title: American Mineralogist
Serial Volume: 88
Serial Issue: 1
Title: Hydration, expansion, structure, and dynamics of layered double hydroxides
Affiliation: University of Illinois at Urbana-Champaign, Department of Geology, Urbana, IL, United States
Pages: 167-179
Published: 200301
Text Language: English
Publisher: Mineralogical Society of America, Washington, DC, United States
References: 62
Accession Number: 2003-024313
Categories: Mineralogy of non-silicates
Document Type: Serial
Bibliographic Level: Analytic
Illustration Description: illus. incl. 2 tables
Secondary Affiliation: Los Alamos National Laboratory, USA, United StatesPurdue University, USA, United States
Country of Publication: United States
Secondary Affiliation: GeoRef, Copyright 2018, American Geosciences Institute.
Update Code: 200309
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