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On the Thermal Stability and Structures of Layered Double Hydroxides Mg 1– x Al x (OH) 2 (NO 3 ) x · m H 2 O (0.18 ≤ x ≤ 0.38)
Author(s) -
Sjåstad Anja Olafsen,
Andersen Niels Højmark,
Vajeeston Ponniah,
Karthikeyan Jayakumar,
Arstad Bjørnar,
Karlsson Arne,
Fjellvåg Helmer
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201403232
Subject(s) - chemistry , crystallography , octahedron , neutron diffraction , x ray crystallography , layered double hydroxides , crystal structure , analytical chemistry (journal) , inorganic chemistry , diffraction , hydroxide , physics , chromatography , optics
Nitrate‐based layered double hydroxides, Mg 1– x Al x (OH) 2 (NO 3 ) x · m H 2 O, have been investigated to settle issues relating to stability towards humidity, dehydration and staging, nitrate group orientation, Al migration and crystal structure. Raman and IR spectroscopy together with modelling methods proved that flat‐lying water and nitrate become tilted towards [001] at higher nitrate concentrations, accompanied by expansion along the c ‐axis. The distribution of the molecular tilts is greatest for x = 0.25, which explains the extraordinary broad diffraction peaks. The unit cell volume was modified for all samples when subjected to moist air, most strongly for x = 0.25. On heating, in situ synchrotron diffraction data showed continuous changes along the c ‐axis during dehydration of samples with x = 0.20 and 0.33. For x = 0.25, an intermediate phase appeared. Dehydroxylation was initiated at the OH groups bonded to the cations MgAl 2 , Mg 2 Al and Mg 3 (in said order), whereas complete nitrate loss occurred at higher temperatures for higher Al contents. Some aluminium simultaneously moved to tetrahedral sites, which, according to 1 H– 27 Al CP NMR spectroscopy, lack protons in their near neighbourhood. In contrast, octahedral aluminium remains surrounded by protons during decomposition. For the metastable oxide product, neutron diffraction indicated that 2/3 of aluminium reside in tetrahedral interstices. This oxide is defective, probably mimicking wüstite rather than a regular rock salt structure.