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

Title data

Shivaramaiah, Radha ; Kumar, Jayanthi ; Breu, Josef ; Kamath, P. Vishnu:
Relative Humidity-Induced Reversible Hydration of Sulfate-Intercalated Layered Double Hydroxides.
In: Clays and Clay Minerals. Vol. 62 (February 2014) Issue 1 . - pp. 53-61.
ISSN 1552-8367
DOI: https://doi.org/10.1346/CCMN.2014.0620105

Official URL: Volltext

Abstract in another language

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.

Further data

Item Type: Article in a journal
Refereed: Yes
Keywords: Cation ordering; Layered double hydroxides; Polytype transformation
Institutions of the University: Faculties
Faculties > Faculty of Biology, Chemistry and Earth Sciences
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Anorganic Chemistry I
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Anorganic Chemistry I > Chair Anorganic Chemistry I - Univ.-Prof. Dr. Josef Breu
Research Institutions > Collaborative Research Centers, Research Unit > SFB 840 Von partikulären Nanosystemen zur Mesotechnologie
Research Institutions
Research Institutions > Collaborative Research Centers, Research Unit
Result of work at the UBT: No
DDC Subjects: 500 Science > 540 Chemistry
Date Deposited: 29 Mar 2018 10:06
Last Modified: 29 Mar 2018 10:06
URI: https://eref.uni-bayreuth.de/id/eprint/43165