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Relative Humidity-Induced Reversible Hydration Of Sulfate-Intercalated Layered Double Hydroxides

Published online by Cambridge University Press:  01 January 2024

S. Radha ,
K. Jayanthi ,
Josef Breu  and
P. Vishnu Kamath
S. Radha
Affiliation:
Department of Chemistry, Central College, Bangalore University, 5600 01, Bangalore, India
K. Jayanthi
Affiliation:
Department of Chemistry, Central College, Bangalore University, 5600 01, Bangalore, India
Josef Breu*
Affiliation:
Department of Inorganic Chemistry I, University of Bayreuth, Bayreuth, Germany
P. Vishnu Kamath*
Affiliation:
Department of Chemistry, Central College, Bangalore University, 5600 01, Bangalore, India
*
*E-mail address of corresponding authors: josef.breu@uni-bayreuth.de, vishnukamath8@hotmail.com
*E-mail address of corresponding authors: josef.breu@uni-bayreuth.de, vishnukamath8@hotmail.com
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Abstract

Layered double hydroxides (LDH) are extremely important materials for industrial processes and in the environment, and their physical-chemical behavior depends in large part on their hydration state, but the characterization of these hydration effects on their properties are incomplete. The present study was designed to explore the interpolytype transitions induced by variation in the ambient humidity among LDHs. The cooperative behavior of intercalated water molecules resulted in a sudden, single-step, reversible dehydration of the [Zn-Cr-SO4] LDH. The [Zn-Al-SO4] LDH provided an interesting contrast with (1) the coexistence of the end members of the hydration cycle over the 40-20% relative humidity range during the dehydration cycle, and (2) a random interstratified intermediate in the hydration cycle. These observations showed that the [Zn-Al-SO4] LDH offered sites having a range of hydration enthalpies, whereby, at critical levels of hydration (20–40%), the non-uniform swelling of the structure resulted in an interstratified phase. The variation in domain size during reversible hydration was also responsible for the differences observed in the hydration vs. the dehydration pathways. This behavior was attributed to the distortion in the array of hydroxyl ions which departs from hexagonal symmetry on account of cation ordering as shown by structure refinement by the Rietveld method. This distortion was much less in the [Zn-Cr-SO4] LDH, whereby the nearly hexagonal array of hydroxyl ions offered sites of uniform hydration enthalpy for the intercalated water molecules. In this case, all the water molecules experienced the same force of attraction and dehydrated reversibly in a single step. The changes in basal spacing were also accompanied by interpolytype transitions, involving the rigid translations of the metal hydroxide layers relative to one another.

Keywords

Cation OrderingLayered Double HydroxidesPolytype Transformation
Type
Article
Information
Clays and Clay Minerals , Volume 62 , Issue 1 , February 2014 , pp. 53 - 61
Copyright
Copyright © Clay Minerals Society 2014

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