In-Situ Studies of Structure Transformation and Al Coordination of KAl(MoO4)2 during Heating by High Temperature Raman and 27Al NMR Spectroscopies

Recent interest in optimizing composition and synthesis conditions of functional crystals, and the further exploration of new possible candidates for tunable solid-state lasers, has led to significant research on compounds in this family MIMIII(MVIO4)2 (MI = alkali metal, MIII = Al, In, Sc, Fe, Bi,...

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Published inMaterials Vol. 10; no. 3; p. 310
Main Authors Wang, Min, You, Jinglin, Sobol, Alexander, Lu, Liming, Wang, Jian, Xie, Yingfang
Format Journal Article
LanguageEnglish
Published Basel MDPI AG 17.03.2017
MDPI
Subjects
27Al MAS NMR
Al coordination environment
Alkali metals
Aluminum
Coordination
double molybdate KAl(MoO4)2
First principles
first principles calculation
High temperature
in-situ Raman spectroscopy
Iron
NMR
NMR spectroscopy
Nuclear magnetic resonance
Raman spectra
Resonance scattering
Room temperature
Solid state lasers
structure transformation
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Abstract Recent interest in optimizing composition and synthesis conditions of functional crystals, and the further exploration of new possible candidates for tunable solid-state lasers, has led to significant research on compounds in this family MIMIII(MVIO4)2 (MI = alkali metal, MIII = Al, In, Sc, Fe, Bi, lanthanide; MVI = Mo, W). The vibrational modes, structure transformation, and Al coordination of crystalline, glassy, and molten states of KAl(MoO4)2 have been investigated by in-situ high temperature Raman scattering and 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, together with first principles density functional simulation of room temperature Raman spectrum. The results showed that, under the present fast quenching conditions, Al is present predominantly in [AlO6] octahedra in both KAl(MoO4)2 glass and melt, with the tetrahedrally coordinated Al being minor at approximately 2.7%. The effect of K+, from ordered arrangement in the crystal to random distribution in the melt, on the local chemical environment of Al, was also revealed. The distribution and quantitative analysis of different Al coordination subspecies are final discussed and found to be dependent on the thermal history of the glass samples.
AbstractList Recent interest in optimizing composition and synthesis conditions of functional crystals, and the further exploration of new possible candidates for tunable solid-state lasers, has led to significant research on compounds in this family MIMIII(MVIO4)2 (MI = alkali metal, MIII = Al, In, Sc, Fe, Bi, lanthanide; MVI = Mo, W). The vibrational modes, structure transformation, and Al coordination of crystalline, glassy, and molten states of KAl(MoO4)2 have been investigated by in-situ high temperature Raman scattering and 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, together with first principles density functional simulation of room temperature Raman spectrum. The results showed that, under the present fast quenching conditions, Al is present predominantly in [AlO6] octahedra in both KAl(MoO4)2 glass and melt, with the tetrahedrally coordinated Al being minor at approximately 2.7%. The effect of K+, from ordered arrangement in the crystal to random distribution in the melt, on the local chemical environment of Al, was also revealed. The distribution and quantitative analysis of different Al coordination subspecies are final discussed and found to be dependent on the thermal history of the glass samples.
Recent interest in optimizing composition and synthesis conditions of functional crystals, and the further exploration of new possible candidates for tunable solid-state lasers, has led to significant research on compounds in this family M I M III (M VI O 4 ) 2 (M I = alkali metal, M III = Al, In, Sc, Fe, Bi, lanthanide; M VI = Mo, W). The vibrational modes, structure transformation, and Al coordination of crystalline, glassy, and molten states of KAl(MoO 4 ) 2 have been investigated by in-situ high temperature Raman scattering and 27 Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, together with first principles density functional simulation of room temperature Raman spectrum. The results showed that, under the present fast quenching conditions, Al is present predominantly in [AlO 6 ] octahedra in both KAl(MoO 4 ) 2 glass and melt, with the tetrahedrally coordinated Al being minor at approximately 2.7%. The effect of K + , from ordered arrangement in the crystal to random distribution in the melt, on the local chemical environment of Al, was also revealed. The distribution and quantitative analysis of different Al coordination subspecies are final discussed and found to be dependent on the thermal history of the glass samples.
Author Wang, Jian
Xie, Yingfang
Wang, Min
You, Jinglin
Lu, Liming
Sobol, Alexander
AuthorAffiliation 2 Prokhorov General Physics Institute, Russian Academy of Sciences, Ulitsa, Vavilova 38, Moscow 119991, Russia
3 CSIRO Mineral Resources, Technology Court, Pullenvale, Queensland 4069, Australia
1 State Key Laboratory of Advanced Special Steel & Shanghai Key Laboratory of Advanced Ferrometallurgy & School of Materials Science and Engineering, Shanghai University, Shanghai 200072, China; wangmin1558@126.com (M.W.); wj581692@126.com (J.W.); yingfangxie@163.com (Y.X.)
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SubjectTerms 27Al MAS NMR
Al coordination environment
Alkali metals
Aluminum
Coordination
double molybdate KAl(MoO4)2
First principles
first principles calculation
High temperature
in-situ Raman spectroscopy
Iron
NMR
NMR spectroscopy
Nuclear magnetic resonance
Raman spectra
Resonance scattering
Room temperature
Solid state lasers
structure transformation
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Title In-Situ Studies of Structure Transformation and Al Coordination of KAl(MoO4)2 during Heating by High Temperature Raman and 27Al NMR Spectroscopies
URI https://www.proquest.com/docview/1888950282
https://search.proquest.com/docview/1926682456
https://pubmed.ncbi.nlm.nih.gov/PMC5503307
https://doaj.org/article/0ff6eec1c6104d13a34b257dfe051cb5
Volume 10
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