Insertion-release of guest species and ionic conduction in polyoxometalate solids with a layer-like Anderson structure

Journal Article · Fri Apr 15 00:00:00 EDT 2011 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2011.01.033· OSTI ID:21494259

Naruke, Haruo ^[1]; Kajitani, Naoyuki ^[1]; Konya, Takayuki ^[2]

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1. Chemical Resources Laboratory, Tokyo Institute of Technology, R1-23, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503 (Japan)
2. Rigaku Corporation, 3-9-12, Matsubara-cho, Akishima-shi, Tokyo 196-8666 (Japan)

The precipitation of Na{sup +} and K{sup +} mixed salts of Anderson type [SbW{sub 6}O{sub 24}]{sup 7-} by addition of excess of NaNO{sub 3} and NaCl yielded polycrystalline powders of Na{sub 2.5}K{sub 5.3}[SbW{sub 6}O{sub 24}](NO{sub 3}){sub 0.8}.12H{sub 2}O (1) and Na{sub 2}K{sub 5.35}[SbW{sub 6}O{sub 24}]Cl{sub 0.35}.12H{sub 2}O (2), respectively. The two compounds are isomorphous and exhibit a layer-like Anderson (LLA) type structure, which consists of [SbW{sub 6}O{sub 24}]{sup 7-}-containing layers and interstitial Na{sup +}, K{sup +}, NO{sub 3}{sup -} or Cl{sup -}, and water O atoms. Recrystallization of 1 and 2 from hot water yielded Na{sub 2}K{sub 5.4}[SbW{sub 6}O{sub 24}](NO{sub 3}){sub 0.4}.12H{sub 2}O (1-recry) and Na{sub 2}K{sub 5.25}[SbW{sub 6}O{sub 24}]Cl{sub 0.25}.12H{sub 2}O (2-recry) as a result of partial release of NO{sub 3}{sup -} and Cl{sup -} (and Na{sup +} and K{sup +} for charge compensation). Dehydration of 1 and 2 at 400 and 500 {sup o}C (1-dehyd400 and 2-dehyd500) caused a shrinkage of lattice, but their the LLA structures retained. Simulation of X-ray diffraction (XRD) patterns for the dehydrated forms allowed to presume that the each [SbW{sub 6}O{sub 24}]{sup 7-} anion had been 30{sup o}-rotated within its molecular plane in order to avoid intermolecular repulsion. A compressed powder of 1-dehyd400 exhibited fast alkaline-ion conduction with a bulk conductivity of 1.2x10{sup -2} {Omega}{sup -1} cm{sup -1} at 400 {sup o}C. The hosting of a sufficient amount of NO{sub 3}{sup -} together with Na{sup +} for charge compensation into the lattice is crucial for high conduction. -- Graphical abstract: Two compounds Na{sub 2.5}K{sub 5.3}[SbW{sub 6}O{sub 24}](NO{sub 3}){sub 0.8}.12H{sub 2}O (1) and Na{sub 2}K{sub 5.35}[SbW{sub 6}O{sub 24}]Cl{sub 0.35}.12H{sub 2}O (2) possessing a layer-like Anderson (LLA) structure exhibited pseudo intercalation-deintercalation behavior. The dehydrated form of 1 is a high alkaline cation conductor with a conductivity of 1.2x10{sup -2} {Omega}{sup -1} cm{sup -1} at 400 {sup o}C. Display Omitted Research highlights: {yields} Layer-like Anderson-type POM solid accommodates and releases NO{sub 3}{sup -} and Cl{sup -}. {yields} The POM exhibits reversible dehydration by heat treatment. {yields} The dehydration involves rotation of POM molecule retaining layer structure. {yields} The dehydrated POM shows good Na{sup +} and K{sup +} conduction.

• OSTI ID: 21494259
• Journal Information: Journal of Solid State Chemistry, Vol. 184, Issue 4; Other Information: DOI: 10.1016/j.jssc.2011.01.033; PII: S0022-4596(11)00044-2; Copyright (c) 2011 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
ANIONS
ANTIMONY COMPOUNDS
CATIONS
CHLORINE IONS
DEHYDRATION
HEAT TREATMENTS
HOT WATER
INTERSTITIALS
LAYERS
POLYCRYSTALS
POTASSIUM IONS
PRECIPITATION
RECRYSTALLIZATION
SIMULATION
SODIUM CHLORIDES
SODIUM IONS
SODIUM NITRATES
SOLIDS
TEMPERATURE RANGE 0400-1000 K
TUNGSTATES
X-RAY DIFFRACTION
ALKALI METAL COMPOUNDS
CHARGED PARTICLES
CHLORIDES
CHLORINE COMPOUNDS
COHERENT SCATTERING
CRYSTAL DEFECTS
CRYSTAL STRUCTURE
CRYSTALS
DIFFRACTION
HALIDES
HALOGEN COMPOUNDS
HYDROGEN COMPOUNDS
IONS
NITRATES
NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
POINT DEFECTS
REFRACTORY METAL COMPOUNDS
SCATTERING
SEPARATION PROCESSES
SODIUM COMPOUNDS
TEMPERATURE RANGE
TRANSITION ELEMENT COMPOUNDS
TUNGSTEN COMPOUNDS
WATER