The defect structure and chemical lattice strain of the double perovskites Sr2BMoO6-δ (B = Mg, Fe) / Tsvetkov D.S., Ivanov I.L., Malyshkin D.A., Steparuk A.S., Zuev A.Yu. // Dalton Transactions. - 2016. - V. 45, l. 32. - P. 12906-12913.

ISSN:

14779226

Type:

Article

Abstract:

The defect structure of B-site ordered double perovskites Sr2BMoO6-δ was analyzed. The defect structure model was proposed and successfully verified using data on oxygen nonstoichiometry of Sr2MgMoO6-δ and Sr2FeMoO6-δ. As a result, equilibrium constants of the defect reactions involved were estimated. Fe and Mo in Sr2FeMoO6-δ were found to be in the mixed oxidation state close to +2.5 and +5.5, respectively. Chemical strain of the Sr2FeMoO6-δ double perovskite lattice was studied by in situ high temperature XRD at 1100 °C depending on pO2. Parameter a of the Sr2FeMoO6-δ cubic cell was found to increase with decreasing pO2 because of lattice chemical expansion. The tetragonal polymorph of Sr2FeMoO6-δ was shown to exhibit transversal isotropy with respect to chemical expansion. It was also found that its crystal lattice expands in the ab-plane and simultaneously contracts along the c-axis when the oxygen content in the double perovskite decreases. In order to describe the degree of anisotropy of chemical strain a new phenomenological coefficient was introduced. This coefficient was shown to affect both the magnitude and change direction of an oxide cell volume caused by its reduction/oxidation. Excellent agreement between the chemical expansion along the a-axis calculated for both polymorphs of Sr2FeMoO6-δ according to the model recently developed and that measured experimentally was shown. Chemical contraction observed along the c-axis with a decreasing oxygen content in the tetragonal polymorph was also found to coincide completely with that calculated using the approach developed in the present study. © 2016 The Royal Society of Chemistry.

Author keywords:

Index keywords:

Defect structures; Defects; Equilibrium constants; Expansion; Oxygen; Strontium compounds; Chemical expansion; Degree of anisotropy; Double perovskites; Ordered double perovskites; Oxygen non-stoichio

DOI:

10.1039/c6dt02513g

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Link	https://www.scopus.com/inward/record.uri?eid=2-s2.0-84982084216&doi=10.1039%2fc6dt02513g&partnerID=40&md5=24b612a7a63e121b3e7b21219757cdeb
Affiliations	Department of Chemistry, Institute of Natural Sciences, Ural Federal University, Ekaterinburg, Russian Federation
Funding Details	15-33-20978, RFBR, Russian Foundation for Basic Research
Funding Text	This work was supported by the Russian Foundation for Basic Research (Grant No. 15-33-20978).
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Correspondence Address	Tsvetkov, D.S.; Department of Chemistry, Institute of Natural Sciences, Ural Federal UniversityRussian Federation; email: dmitry.tsvetkov@urfu.ru
Publisher	Royal Society of Chemistry
CODEN	DTARA
Language of Original Document	English
Abbreviated Source Title	Dalton Trans.
Source	Scopus