Comprehensive Study of Oxygen Storage in YbFe2 O4+x (x ≤ 0.5): Unprecedented Coexistence of FeOn Polyhedra in One Single Phase

Journal of the American Chemical Society
Sarah NicoudOlivier Mentré

Abstract

The multiferroic LuFe2.5+2O4 was recently proposed as a promising material for oxygen storage due to its easy reversible oxidation into LuFe3+2O4.5. We have investigated the similar scenario in YbFe2O4+x, leading to a slightly greater oxygen storage (OSC) capacity of 1434 μmol O/g. For the first time, the structural model of LnFe2O4.5 was fully understood by high-resolution microscopy images, and synchrotron and neutron diffraction experiments, as well as maximum entropy method. The oxygen uptake promotes a reconstructive shearing of the [YbO2] sub-units controlled by the adaptive Ln/Fe oxygen coordination and the Fe2/3+ redox. After oxidation, the rearrangement of the Fe coordination polyhedra is unique such that all available FeOn units (n = 6, 5, 4 in octahedra, square pyramids, trigonal bipyramids, tetrahedra) were identified in modulated rows growing in plane. This complex pseudo-ordering gives rise to short-range antiferromagnetic correlation within an insulating state.

References

Sep 10, 2004·Nature·Zongping Shao, Sossina M Haile
May 4, 2005·Nature Materials·Antonino Salvatore AricòWalter van Schalkwijk
Aug 7, 2007·Physical Review Letters·Y ZhangJ Q Li
Mar 21, 2008·Physical Review Letters·A D ChristiansonD Mandrus
Oct 28, 2014·Angewandte Chemie·Rénald DavidOlivier Mentré

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