The Electrical and Structural Characterization of Ba3Mo1-xNb1+xO8.5-x/2: The relationship between mixed coordination, polyhedral distortion and the ionic conductivity of Ba3MoNbO8.5

Sacha Fop; Eve J. Wildman; Jan M. S. Skakle; Clemens  Ritter; Abbie C. McLaughlin

doi:10.1021/acs.inorgchem.7b01488

The Electrical and Structural Characterization of Ba3Mo1-xNb1+xO8.5-x/2: The relationship between mixed coordination, polyhedral distortion and the ionic conductivity of Ba3MoNbO8.5

Sacha Fop, Eve J. Wildman, Jan M. S. Skakle, Clemens Ritter, Abbie C. McLaughlin

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Abstract

The electrical and structural properties of the series Ba3Mo1-xNb1+xO8.5-x/2 (x = 0.0, 0.1, 0.2, 0.3) have been determined. Ba3Mo1-xNb1+xO8.5-x/2 crystallises in a hybrid of the 9R hexagonal perovskite and palmierite structures, in which (Mo/Nb)O4 and (Mo/Nb)O6 units coexist within the structure. Nb substitutes preferentially at the octahedral site so that the ratio of (Mo/Nb)O4 tetrahedra to (Mo/Nb)O6 octahedra decreases with increasing x resulting in a reduction in the magnitude of the ionic conductivity from 1.3 × 10-6 S cm-1 for x = 0.0 to 1.1 × 10-7 S cm-1 for x = 0.3 at 300 °C. However upon heating the conductivities of the solid solution converge, which suggests that the unusual thermal structural rearrangement previously reported for Ba3MoNbO8 preserves the high temperature conductivity. The results demonstrate that the presence of (Mo/Nb)O4 tetrahedra with non-bridging apical oxygen atoms is an important prerequisite for the ionic conduction observed in the Ba3MoNbO8.5 system.

Original language	English
Pages (from-to)	10505-10512
Number of pages	8
Journal	Inorganic Chemistry
Volume	56
Issue number	17
Early online date	17 Aug 2017
DOIs	https://doi.org/10.1021/acs.inorgchem.7b01488
Publication status	Published - 2017

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This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.7b01488
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The Electrical and Structural Characterization of Ba3Mo1-xNb1+xO8.5-x/2 : The relationship between mixed coordination, polyhedral distortion and the ionic conductivity of Ba3MoNbO8.5. / Fop, Sacha; Wildman, Eve J.; Skakle, Jan M. S. et al.

In: Inorganic Chemistry, Vol. 56, No. 17, 2017, p. 10505-10512.

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

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title = "The Electrical and Structural Characterization of Ba3Mo1-xNb1+xO8.5-x/2: The relationship between mixed coordination, polyhedral distortion and the ionic conductivity of Ba3MoNbO8.5",

abstract = "The electrical and structural properties of the series Ba3Mo1-xNb1+xO8.5-x/2 (x = 0.0, 0.1, 0.2, 0.3) have been determined. Ba3Mo1-xNb1+xO8.5-x/2 crystallises in a hybrid of the 9R hexagonal perovskite and palmierite structures, in which (Mo/Nb)O4 and (Mo/Nb)O6 units coexist within the structure. Nb substitutes preferentially at the octahedral site so that the ratio of (Mo/Nb)O4 tetrahedra to (Mo/Nb)O6 octahedra decreases with increasing x resulting in a reduction in the magnitude of the ionic conductivity from 1.3 × 10-6 S cm-1 for x = 0.0 to 1.1 × 10-7 S cm-1 for x = 0.3 at 300 °C. However upon heating the conductivities of the solid solution converge, which suggests that the unusual thermal structural rearrangement previously reported for Ba3MoNbO8 preserves the high temperature conductivity. The results demonstrate that the presence of (Mo/Nb)O4 tetrahedra with non-bridging apical oxygen atoms is an important prerequisite for the ionic conduction observed in the Ba3MoNbO8.5 system.",

author = "Sacha Fop and Wildman, {Eve J.} and Skakle, {Jan M. S.} and Clemens Ritter and McLaughlin, {Abbie C.}",

note = "This research was supported by the Northern Research Partnership and the University of Aberdeen. We also acknowledge STFC-GB for provision of beamtime at the ILL.",

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T1 - The Electrical and Structural Characterization of Ba3Mo1-xNb1+xO8.5-x/2

T2 - The relationship between mixed coordination, polyhedral distortion and the ionic conductivity of Ba3MoNbO8.5

AU - Fop, Sacha

AU - Wildman, Eve J.

AU - Skakle, Jan M. S.

AU - Ritter, Clemens

AU - McLaughlin, Abbie C.

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PY - 2017

Y1 - 2017

N2 - The electrical and structural properties of the series Ba3Mo1-xNb1+xO8.5-x/2 (x = 0.0, 0.1, 0.2, 0.3) have been determined. Ba3Mo1-xNb1+xO8.5-x/2 crystallises in a hybrid of the 9R hexagonal perovskite and palmierite structures, in which (Mo/Nb)O4 and (Mo/Nb)O6 units coexist within the structure. Nb substitutes preferentially at the octahedral site so that the ratio of (Mo/Nb)O4 tetrahedra to (Mo/Nb)O6 octahedra decreases with increasing x resulting in a reduction in the magnitude of the ionic conductivity from 1.3 × 10-6 S cm-1 for x = 0.0 to 1.1 × 10-7 S cm-1 for x = 0.3 at 300 °C. However upon heating the conductivities of the solid solution converge, which suggests that the unusual thermal structural rearrangement previously reported for Ba3MoNbO8 preserves the high temperature conductivity. The results demonstrate that the presence of (Mo/Nb)O4 tetrahedra with non-bridging apical oxygen atoms is an important prerequisite for the ionic conduction observed in the Ba3MoNbO8.5 system.

AB - The electrical and structural properties of the series Ba3Mo1-xNb1+xO8.5-x/2 (x = 0.0, 0.1, 0.2, 0.3) have been determined. Ba3Mo1-xNb1+xO8.5-x/2 crystallises in a hybrid of the 9R hexagonal perovskite and palmierite structures, in which (Mo/Nb)O4 and (Mo/Nb)O6 units coexist within the structure. Nb substitutes preferentially at the octahedral site so that the ratio of (Mo/Nb)O4 tetrahedra to (Mo/Nb)O6 octahedra decreases with increasing x resulting in a reduction in the magnitude of the ionic conductivity from 1.3 × 10-6 S cm-1 for x = 0.0 to 1.1 × 10-7 S cm-1 for x = 0.3 at 300 °C. However upon heating the conductivities of the solid solution converge, which suggests that the unusual thermal structural rearrangement previously reported for Ba3MoNbO8 preserves the high temperature conductivity. The results demonstrate that the presence of (Mo/Nb)O4 tetrahedra with non-bridging apical oxygen atoms is an important prerequisite for the ionic conduction observed in the Ba3MoNbO8.5 system.

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The Electrical and Structural Characterization of Ba3Mo1-xNb1+xO8.5-x/2: The relationship between mixed coordination, polyhedral distortion and the ionic conductivity of Ba3MoNbO8.5

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The Electrical and Structural Characterization of Ba3Mo1-xNb1+xO8.5-x/2: The relationship between mixed coordination, polyhedral distortion and the ionic conductivity of Ba3MoNbO8.5

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