Investigation of the hydrothermal crystallisation of the perovskite solid solution NaCe1-xLaxTi2O6 and its defect chemistry

Mohammad H. Harunsani; David I. Woodward; Martin Peel; Sharon Elizabeth Ashbrook; Richard I. Walton

doi:10.1016/j.jssc.2013.09.015

Investigation of the hydrothermal crystallisation of the perovskite solid solution NaCe_1-xLa_xTi₂O₆and its defect chemistry

Mohammad H. Harunsani, David I. Woodward, Martin Peel, Sharon Elizabeth Ashbrook, Richard I. Walton^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

Perovskites of nominal composition NaCe_1−xLa_xTi₂O₆ (0≤x≤1) crystallise directly under hydrothermal conditions at 240 °C. Raman spectroscopy shows distortion from the ideal cubic structure and Rietveld analysis of powder X-ray and neutron diffraction reveals that the materials represent a continuous series in rhombohedral space group R3̄c. Ce L_III-edge X-ray absorption near edge structure spectroscopy shows that while the majority of cerium is present as Ce³⁺ there is evidence for Ce⁴⁺. The paramagnetic Ce³⁺ affects the chemical shift and line width of ²³Na MAS NMR spectra, which also show with no evidence for A-site ordering. ²H MAS NMR of samples prepared in D₂O shows the inclusion of deuterium, which IR spectroscopy shows is most likely to be as D₂O. The deuterium content is highest for the cerium-rich materials, consistent with oxidation of some cerium to Ce⁴⁺ to provide charge balance of A-site water.

Original language	English
Pages (from-to)	117-125
Number of pages	9
Journal	Journal of Solid State Chemistry
Volume	207
Early online date	20 Sept 2013
DOIs	https://doi.org/10.1016/j.jssc.2013.09.015
Publication status	Published - Nov 2013

Keywords

Perovskite
Hydrothermal
XANES
NMR
Neutron diffraction
Free piezoelectric ceramics
Low-temperature
X-ray
Oxidation-state
Barium-titanate
Thin-films
LA1/2NA1/2TIO3 NANOCRYSTALS
Quantum paraelectricity
Raman-spectroscopy
BATIO3

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10.1016/j.jssc.2013.09.015

harunsani2013jsolidstatechem117
© 2013. Elsevier Inc. All rights reserved. This is the author’s version of a work that was accepted for publication in Journal of Solid State Chemistry. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Journal of Solid State Chemistry, 203, November 2013 DOI 10.1016/j.jssc.2013.09.015
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Cite this

@article{14e39a2adc184a4f91fe27f3ccee729a,

title = "Investigation of the hydrothermal crystallisation of the perovskite solid solution NaCe1-xLaxTi2O6 and its defect chemistry",

abstract = "Perovskites of nominal composition NaCe1−xLaxTi2O6 (0≤x≤1) crystallise directly under hydrothermal conditions at 240 °C. Raman spectroscopy shows distortion from the ideal cubic structure and Rietveld analysis of powder X-ray and neutron diffraction reveals that the materials represent a continuous series in rhombohedral space group R{\=3}c. Ce LIII-edge X-ray absorption near edge structure spectroscopy shows that while the majority of cerium is present as Ce3+ there is evidence for Ce4+. The paramagnetic Ce3+ affects the chemical shift and line width of 23Na MAS NMR spectra, which also show with no evidence for A-site ordering. 2H MAS NMR of samples prepared in D2O shows the inclusion of deuterium, which IR spectroscopy shows is most likely to be as D2O. The deuterium content is highest for the cerium-rich materials, consistent with oxidation of some cerium to Ce4+ to provide charge balance of A-site water. ",

keywords = "Perovskite, Hydrothermal, XANES, NMR, Neutron diffraction, Free piezoelectric ceramics, Low-temperature, X-ray, Oxidation-state, Barium-titanate, Thin-films, LA1/2NA1/2TIO3 NANOCRYSTALS, Quantum paraelectricity, Raman-spectroscopy, BATIO3",

author = "Harunsani, {Mohammad H.} and Woodward, {David I.} and Martin Peel and Ashbrook, {Sharon Elizabeth} and Walton, {Richard I.}",

note = "MHH thanks the Ministry of Education, Brunei for award of a scholarship. EPSRC are thanked for a DTG studentship to MDP. ",

year = "2013",

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doi = "10.1016/j.jssc.2013.09.015",

language = "English",

volume = "207",

pages = "117--125",

journal = "Journal of Solid State Chemistry",

issn = "0022-4596",

publisher = "Academic Press/Elsevier ",

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T1 - Investigation of the hydrothermal crystallisation of the perovskite solid solution NaCe1-xLaxTi2O6 and its defect chemistry

AU - Harunsani, Mohammad H.

AU - Woodward, David I.

AU - Peel, Martin

AU - Ashbrook, Sharon Elizabeth

AU - Walton, Richard I.

N1 - MHH thanks the Ministry of Education, Brunei for award of a scholarship. EPSRC are thanked for a DTG studentship to MDP.

PY - 2013/11

Y1 - 2013/11

N2 - Perovskites of nominal composition NaCe1−xLaxTi2O6 (0≤x≤1) crystallise directly under hydrothermal conditions at 240 °C. Raman spectroscopy shows distortion from the ideal cubic structure and Rietveld analysis of powder X-ray and neutron diffraction reveals that the materials represent a continuous series in rhombohedral space group R3̄c. Ce LIII-edge X-ray absorption near edge structure spectroscopy shows that while the majority of cerium is present as Ce3+ there is evidence for Ce4+. The paramagnetic Ce3+ affects the chemical shift and line width of 23Na MAS NMR spectra, which also show with no evidence for A-site ordering. 2H MAS NMR of samples prepared in D2O shows the inclusion of deuterium, which IR spectroscopy shows is most likely to be as D2O. The deuterium content is highest for the cerium-rich materials, consistent with oxidation of some cerium to Ce4+ to provide charge balance of A-site water.

AB - Perovskites of nominal composition NaCe1−xLaxTi2O6 (0≤x≤1) crystallise directly under hydrothermal conditions at 240 °C. Raman spectroscopy shows distortion from the ideal cubic structure and Rietveld analysis of powder X-ray and neutron diffraction reveals that the materials represent a continuous series in rhombohedral space group R3̄c. Ce LIII-edge X-ray absorption near edge structure spectroscopy shows that while the majority of cerium is present as Ce3+ there is evidence for Ce4+. The paramagnetic Ce3+ affects the chemical shift and line width of 23Na MAS NMR spectra, which also show with no evidence for A-site ordering. 2H MAS NMR of samples prepared in D2O shows the inclusion of deuterium, which IR spectroscopy shows is most likely to be as D2O. The deuterium content is highest for the cerium-rich materials, consistent with oxidation of some cerium to Ce4+ to provide charge balance of A-site water.

KW - Perovskite

KW - Hydrothermal

KW - XANES

KW - NMR

KW - Neutron diffraction

KW - Free piezoelectric ceramics

KW - Low-temperature

KW - X-ray

KW - Oxidation-state

KW - Barium-titanate

KW - Thin-films

KW - LA1/2NA1/2TIO3 NANOCRYSTALS

KW - Quantum paraelectricity

KW - Raman-spectroscopy

KW - BATIO3

U2 - 10.1016/j.jssc.2013.09.015

DO - 10.1016/j.jssc.2013.09.015

M3 - Article

SN - 0022-4596

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SP - 117

EP - 125

JO - Journal of Solid State Chemistry

JF - Journal of Solid State Chemistry

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