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Materials 2016, 9(7), 587; doi:10.3390/ma9070587

Effect of Transition Metal Substitution on the Structure and Properties of a Clathrate-Like Compound Eu7Cu44As23

1
Department of Chemistry, Lomonosov Moscow State University, Moscow 119991, Russia
2
National Institute of Chemical Physics and Biophysics, Tallinn 12618, Estonia
3
Experimental Physics VI, Center for Correlations and Magnetism, Institute of Physics, University of Augsburg, Augsburg 86135, Germany
*
Author to whom correspondence should be addressed.
Academic Editor: Matt Beekman
Received: 9 June 2016 / Revised: 6 July 2016 / Accepted: 14 July 2016 / Published: 19 July 2016
(This article belongs to the Special Issue Inorganic Clathrate Materials)
View Full-Text   |   Download PDF [4304 KB, uploaded 19 July 2016]   |  

Abstract

A series of substitutional solid solutions—Eu7Cu44−xTxAs23 (T = Fe, Co, Ni)—based on a recently discovered clathrate-like compound (Eu7Cu44As23) were synthesized from the elements at 800 °C. Almost up to 50% of Cu can be substituted by Ni, resulting in a linear decrease of the cubic unit cell parameter from a = 16.6707(1) Å for the ternary compound to a = 16.3719(1) Å for the sample with the nominal composition Eu7Cu24Ni20As23. In contrast, Co and Fe can only substitute less than 20% of Cu. Crystal structures of six samples of different composition were refined from powder diffraction data. Despite very small differences in scattering powers of Cu, Ni, Co, and Fe, we were able to propose a reasonable model of dopant distribution over copper sites based on the trends in interatomic distances as well as on Mössbauer spectra for the iron-substituted compound Eu7Cu36Fe8As23. Ni doping increases the Curie temperature to 25 K with respect to the parent compound, which is ferromagnetically ordered below 17.5 K, whereas Fe doping suppresses the ferromagnetic ordering in the Eu sublattice. View Full-Text
Keywords: clathrate; synthesis; crystal structure; magnetic properties; energy production; conversion; storage clathrate; synthesis; crystal structure; magnetic properties; energy production; conversion; storage
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

Plokhikh, I.V.; Charkin, D.O.; Verchenko, V.Y.; Ignatyev, I.A.; Kazakov, S.M.; Sobolev, A.V.; Presniakov, I.A.; Tsirlin, A.A.; Shevelkov, A.V. Effect of Transition Metal Substitution on the Structure and Properties of a Clathrate-Like Compound Eu7Cu44As23. Materials 2016, 9, 587.

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