High-Resolution Thermochemical Study of Phase Stability and Rapid Oxygen Incorporation in YBaCo                         4- x                         Zn                         x                         O                         7+δ                          114-Cobaltites

D. S. Tsvetkov; P. S. Maram; N. S. Tsvetkova; A. Yu Zuev; A. Navrotsky

doi:10.1021/acs.jpca.8b08987

High-Resolution Thermochemical Study of Phase Stability and Rapid Oxygen Incorporation in YBaCo _{4- x} Zn _x O _7+δ 114-Cobaltites

D. S. Tsvetkov, P. S. Maram, N. S. Tsvetkova, A. Yu Zuev, A. Navrotsky

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

4 Scopus citations

Abstract

The formation thermodynamics of YBaCo _4-x Zn _x O _7+δ (x = 0, 1, and 3) oxides was determined by high-temperature oxide melt solution calorimetry. All of the studied oxides are thermodynamically metastable due to the tendency of cobalt to increase the oxidation state under oxidizing conditions as well as to significant bond valence sum mismatch for Ba and Y in 114-oxides. Complex phase evolution in YBaCo ₄ O _7+δ at 350-400 °C upon oxygen absorption was revealed using incremental precise oxygen dosing. The calorimetric results support phase changes seen during in situ X-ray diffraction structural studies and provide high-resolution measurement of the amount and energetics of oxygen absorbed by YBaCo _4-x Zn _x O _7+δ under equilibrium conditions.

Original language	English (US)
Pages (from-to)	9597-9604
Number of pages	8
Journal	Journal of Physical Chemistry A
Volume	122
Issue number	50
DOIs	https://doi.org/10.1021/acs.jpca.8b08987
State	Published - Dec 20 2018
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry

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10.1021/acs.jpca.8b08987

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Tsvetkov, D. S., Maram, P. S., Tsvetkova, N. S., Zuev, A. Y., & Navrotsky, A. (2018). High-Resolution Thermochemical Study of Phase Stability and Rapid Oxygen Incorporation in YBaCo _{4- x} Zn _x O _7+δ 114-Cobaltites Journal of Physical Chemistry A, 122(50), 9597-9604. https://doi.org/10.1021/acs.jpca.8b08987

High-Resolution Thermochemical Study of Phase Stability and Rapid Oxygen Incorporation in YBaCo _{4- x} Zn _x O _7+δ 114-Cobaltites . / Tsvetkov, D. S.; Maram, P. S.; Tsvetkova, N. S. et al.
In: Journal of Physical Chemistry A, Vol. 122, No. 50, 20.12.2018, p. 9597-9604.

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

Tsvetkov, DS, Maram, PS, Tsvetkova, NS, Zuev, AY & Navrotsky, A 2018, ' High-Resolution Thermochemical Study of Phase Stability and Rapid Oxygen Incorporation in YBaCo _{4- x} Zn _x O _7+δ 114-Cobaltites ', Journal of Physical Chemistry A, vol. 122, no. 50, pp. 9597-9604. https://doi.org/10.1021/acs.jpca.8b08987

Tsvetkov DS, Maram PS, Tsvetkova NS, Zuev AY, Navrotsky A. High-Resolution Thermochemical Study of Phase Stability and Rapid Oxygen Incorporation in YBaCo _{4- x} Zn _x O _7+δ 114-Cobaltites Journal of Physical Chemistry A. 2018 Dec 20;122(50):9597-9604. doi: 10.1021/acs.jpca.8b08987

Tsvetkov, D. S. ; Maram, P. S. ; Tsvetkova, N. S. et al. / High-Resolution Thermochemical Study of Phase Stability and Rapid Oxygen Incorporation in YBaCo _{4- x} Zn _x O _7+δ 114-Cobaltites In: Journal of Physical Chemistry A. 2018 ; Vol. 122, No. 50. pp. 9597-9604.

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title = " High-Resolution Thermochemical Study of Phase Stability and Rapid Oxygen Incorporation in YBaCo 4- x Zn x O 7+δ 114-Cobaltites ",

abstract = " The formation thermodynamics of YBaCo 4-x Zn x O 7+δ (x = 0, 1, and 3) oxides was determined by high-temperature oxide melt solution calorimetry. All of the studied oxides are thermodynamically metastable due to the tendency of cobalt to increase the oxidation state under oxidizing conditions as well as to significant bond valence sum mismatch for Ba and Y in 114-oxides. Complex phase evolution in YBaCo 4 O 7+δ at 350-400 °C upon oxygen absorption was revealed using incremental precise oxygen dosing. The calorimetric results support phase changes seen during in situ X-ray diffraction structural studies and provide high-resolution measurement of the amount and energetics of oxygen absorbed by YBaCo 4-x Zn x O 7+δ under equilibrium conditions. ",

author = "Tsvetkov, {D. S.} and Maram, {P. S.} and Tsvetkova, {N. S.} and Zuev, {A. Yu} and A. Navrotsky",

note = "Funding Information: D.S.T. and A.Y.Z. acknowledge financial support from the Ural Federal University within the framework of Act 211 of the Government of the Russian Federation, Agreement No. 02.A03.21.0006. N.S.T. acknowledges the project SP-3440.2016.1 funded by the President of the Russian Federation. The thermochemistry work at Davis was supported by U.S. Department of Energy Grant DE-FG02-03ER46053. Publisher Copyright: {\textcopyright} Copyright 2018 American Chemical Society.",

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AU - Zuev, A. Yu

AU - Navrotsky, A.

N1 - Funding Information: D.S.T. and A.Y.Z. acknowledge financial support from the Ural Federal University within the framework of Act 211 of the Government of the Russian Federation, Agreement No. 02.A03.21.0006. N.S.T. acknowledges the project SP-3440.2016.1 funded by the President of the Russian Federation. The thermochemistry work at Davis was supported by U.S. Department of Energy Grant DE-FG02-03ER46053. Publisher Copyright: © Copyright 2018 American Chemical Society.

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N2 - The formation thermodynamics of YBaCo 4-x Zn x O 7+δ (x = 0, 1, and 3) oxides was determined by high-temperature oxide melt solution calorimetry. All of the studied oxides are thermodynamically metastable due to the tendency of cobalt to increase the oxidation state under oxidizing conditions as well as to significant bond valence sum mismatch for Ba and Y in 114-oxides. Complex phase evolution in YBaCo 4 O 7+δ at 350-400 °C upon oxygen absorption was revealed using incremental precise oxygen dosing. The calorimetric results support phase changes seen during in situ X-ray diffraction structural studies and provide high-resolution measurement of the amount and energetics of oxygen absorbed by YBaCo 4-x Zn x O 7+δ under equilibrium conditions.

AB - The formation thermodynamics of YBaCo 4-x Zn x O 7+δ (x = 0, 1, and 3) oxides was determined by high-temperature oxide melt solution calorimetry. All of the studied oxides are thermodynamically metastable due to the tendency of cobalt to increase the oxidation state under oxidizing conditions as well as to significant bond valence sum mismatch for Ba and Y in 114-oxides. Complex phase evolution in YBaCo 4 O 7+δ at 350-400 °C upon oxygen absorption was revealed using incremental precise oxygen dosing. The calorimetric results support phase changes seen during in situ X-ray diffraction structural studies and provide high-resolution measurement of the amount and energetics of oxygen absorbed by YBaCo 4-x Zn x O 7+δ under equilibrium conditions.

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High-Resolution Thermochemical Study of Phase Stability and Rapid Oxygen Incorporation in YBaCo _{4- x} Zn _x O _7+δ 114-Cobaltites

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