An Investigation of the Crystal Structure and Ionic Pathways of the Hexagonal Perovskite Derivative Ba3-xVMoO8.5

Dylan Tawse; Asma Gilane; Sacha Fop; Alfonso Martinez-Felipe; Falak Sher; Ronald I. Smith; Abbie McLaughlin

doi:10.1021/acs.inorgchem.1c01840

An Investigation of the Crystal Structure and Ionic Pathways of the Hexagonal Perovskite Derivative Ba3-xVMoO8.5

Dylan Tawse, Asma Gilane, Sacha Fop, Alfonso Martinez-Felipe, Falak Sher, Ronald I. Smith, Abbie McLaughlin^* (Corresponding Author)

^*Corresponding author for this work

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

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Abstract

The hexagonal perovskite derivatives Ba3NbMoO8.5, Ba3NbWO8.5 and Ba3VWO8.5 have recently been reported to exhibit significant oxide ion conductivity. Here we report the synthesis and crystal structure of the hexagonal perovskite derivative Ba3-xVMoO8.5-x. Rietveld refinement from neutron and
X-ray diffraction data show that the cation vacancies are ordered on the M2 site leading to a structure consisting of palmierite-like layers of M1Ox polyhedra separated by vacant octahedral layers. In contrast to other members of the Ba3M’M’’O8.5 family, Ba3-xVMoO8.5-x is not stoichiometric and both
barium and oxygen vacancies are present. Although synthesised in air at elevated temperatures, Ba3-xVMoO8.5-x is unstable at lower temperatures, as illustrated by the formation of BaCO3 and BaMoO4 by heat treatment in air at 400 °C. This precludes measurement of the electrical properties. However,
bond-valence site energy (BVSE) calculations strongly suggest that oxide ion conductivity is present in Ba3-xVMoO8.5-x.

Original language	English
Pages (from-to)	13550-13556
Number of pages	7
Journal	Inorganic Chemistry
Volume	60
Early online date	18 Aug 2021
DOIs	https://doi.org/10.1021/acs.inorgchem.1c01840
Publication status	Published - 6 Sept 2021

Bibliographical note

Acknowledgements
We thank the UK Science and Technology Facilities Council (STFC) for provision of Xpress Access neutron beamtime at ISIS. This research was supported by the Leverhulme trust (RPG-2017-351 and DS-2017-073). DNT, a Leverhulme Trust Doctoral Scholar, is part of the PhD scholarships of the “Leverhulme Centre for Doctoral Training in Sustainable Production of Chemicals and Materials” at
the University of Aberdeen (Scotland, United Kingdom). AG is supported by the Commonwealth Scholarship Commission.

Data Availability Statement

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.1c01840.

Keywords

Oxides
Crystal structure
Ions
Oxygen
Perovskites

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Cite this

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title = "An Investigation of the Crystal Structure and Ionic Pathways of the Hexagonal Perovskite Derivative Ba3-xVMoO8.5",

abstract = "The hexagonal perovskite derivatives Ba3NbMoO8.5, Ba3NbWO8.5 and Ba3VWO8.5 have recently been reported to exhibit significant oxide ion conductivity. Here we report the synthesis and crystal structure of the hexagonal perovskite derivative Ba3-xVMoO8.5-x. Rietveld refinement from neutron andX-ray diffraction data show that the cation vacancies are ordered on the M2 site leading to a structure consisting of palmierite-like layers of M1Ox polyhedra separated by vacant octahedral layers. In contrast to other members of the Ba3M{\textquoteright}M{\textquoteright}{\textquoteright}O8.5 family, Ba3-xVMoO8.5-x is not stoichiometric and bothbarium and oxygen vacancies are present. Although synthesised in air at elevated temperatures, Ba3-xVMoO8.5-x is unstable at lower temperatures, as illustrated by the formation of BaCO3 and BaMoO4 by heat treatment in air at 400 °C. This precludes measurement of the electrical properties. However,bond-valence site energy (BVSE) calculations strongly suggest that oxide ion conductivity is present in Ba3-xVMoO8.5-x.",

keywords = "Oxides, Crystal structure, Ions, Oxygen, Perovskites",

author = "Dylan Tawse and Asma Gilane and Sacha Fop and Alfonso Martinez-Felipe and Falak Sher and Smith, {Ronald I.} and Abbie McLaughlin",

note = "Acknowledgements We thank the UK Science and Technology Facilities Council (STFC) for provision of Xpress Access neutron beamtime at ISIS. This research was supported by the Leverhulme trust (RPG-2017-351 and DS-2017-073). DNT, a Leverhulme Trust Doctoral Scholar, is part of the PhD scholarships of the “Leverhulme Centre for Doctoral Training in Sustainable Production of Chemicals and Materials” at the University of Aberdeen (Scotland, United Kingdom). AG is supported by the Commonwealth Scholarship Commission. ",

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T1 - An Investigation of the Crystal Structure and Ionic Pathways of the Hexagonal Perovskite Derivative Ba3-xVMoO8.5

AU - Tawse, Dylan

AU - Gilane, Asma

AU - Fop, Sacha

AU - Martinez-Felipe, Alfonso

AU - Sher, Falak

AU - Smith, Ronald I.

AU - McLaughlin, Abbie

N1 - Acknowledgements We thank the UK Science and Technology Facilities Council (STFC) for provision of Xpress Access neutron beamtime at ISIS. This research was supported by the Leverhulme trust (RPG-2017-351 and DS-2017-073). DNT, a Leverhulme Trust Doctoral Scholar, is part of the PhD scholarships of the “Leverhulme Centre for Doctoral Training in Sustainable Production of Chemicals and Materials” at the University of Aberdeen (Scotland, United Kingdom). AG is supported by the Commonwealth Scholarship Commission.

PY - 2021/9/6

Y1 - 2021/9/6

N2 - The hexagonal perovskite derivatives Ba3NbMoO8.5, Ba3NbWO8.5 and Ba3VWO8.5 have recently been reported to exhibit significant oxide ion conductivity. Here we report the synthesis and crystal structure of the hexagonal perovskite derivative Ba3-xVMoO8.5-x. Rietveld refinement from neutron andX-ray diffraction data show that the cation vacancies are ordered on the M2 site leading to a structure consisting of palmierite-like layers of M1Ox polyhedra separated by vacant octahedral layers. In contrast to other members of the Ba3M’M’’O8.5 family, Ba3-xVMoO8.5-x is not stoichiometric and bothbarium and oxygen vacancies are present. Although synthesised in air at elevated temperatures, Ba3-xVMoO8.5-x is unstable at lower temperatures, as illustrated by the formation of BaCO3 and BaMoO4 by heat treatment in air at 400 °C. This precludes measurement of the electrical properties. However,bond-valence site energy (BVSE) calculations strongly suggest that oxide ion conductivity is present in Ba3-xVMoO8.5-x.

AB - The hexagonal perovskite derivatives Ba3NbMoO8.5, Ba3NbWO8.5 and Ba3VWO8.5 have recently been reported to exhibit significant oxide ion conductivity. Here we report the synthesis and crystal structure of the hexagonal perovskite derivative Ba3-xVMoO8.5-x. Rietveld refinement from neutron andX-ray diffraction data show that the cation vacancies are ordered on the M2 site leading to a structure consisting of palmierite-like layers of M1Ox polyhedra separated by vacant octahedral layers. In contrast to other members of the Ba3M’M’’O8.5 family, Ba3-xVMoO8.5-x is not stoichiometric and bothbarium and oxygen vacancies are present. Although synthesised in air at elevated temperatures, Ba3-xVMoO8.5-x is unstable at lower temperatures, as illustrated by the formation of BaCO3 and BaMoO4 by heat treatment in air at 400 °C. This precludes measurement of the electrical properties. However,bond-valence site energy (BVSE) calculations strongly suggest that oxide ion conductivity is present in Ba3-xVMoO8.5-x.

KW - Oxides

KW - Crystal structure

KW - Ions

KW - Oxygen

KW - Perovskites

U2 - 10.1021/acs.inorgchem.1c01840

DO - 10.1021/acs.inorgchem.1c01840

M3 - Article

SN - 0020-1669

VL - 60

SP - 13550

EP - 13556

JO - Inorganic Chemistry

JF - Inorganic Chemistry

ER -

An Investigation of the Crystal Structure and Ionic Pathways of the Hexagonal Perovskite Derivative Ba3-xVMoO8.5

Abstract

Bibliographical note

Data Availability Statement

Keywords

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