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A 17O Paramagnetic NMR Study of Sm2O3, Eu2O3, and Sm-/Eu- Substituted CeO2

Accepted version
Peer-reviewed

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Authors

Halat, David M 
Lee, Jeongjae 
Grey, Clare P 

Abstract

Paramagnetic solid-state NMR of lanthanide (Ln) containing materials can be challenging due to the high electron spin states possible for the Ln f electrons, which result in large paramagnetic shifts, and these difficulties are compounded for 17O due to the low natural abundance and quadrupolar character. In this work, we present examples of 17O NMR experiments for lanthanide oxides and strategies to overcome these difficulties. In particular, we record and assign the 17O NMR spectra of monoclinic Sm2O3 and Eu2O3 for the first time, as well as performing density functional theory (DFT) calculations to gain further insight into the spectra. The temperature dependence of the Sm3+ and Eu3+ magnetic susceptibilities are investigated by measuring the 17O shift of the cubic sesquioxides over a wide temperature range, which reveal non-Curie temperature dependence due to the presence of low-lying electronic states. This behaviour is reproduced by calculating the electron spin as a function of temperature, yielding shifts which agree well with the experimental values. Using the understanding of the magnetic behaviour gained from the sesquioxides, we then explore the local oxygen environments in 15 at% Sm- and Eu-substituted CeO2, with the 17O NMR spectrum exhibiting signals due to environments with zero, one and two nearest neighbour Ln ions, as well as further splitting due to oxygen vacancies. Finally, we extract an activation energy for oxygen vacancy motion in these systems of 0.35 ± 0.02 eV from the Arrhenius temperature dependence of the 17O T1 relaxation constants, which is found to be independent of the Ln ion within error. The relation of this activation energy to literature values for oxygen diffusion in Ln-substituted CeO2 is discussed to infer mechanistic information which can be applied to further develop these materials as solid-state oxide-ion conductors.

Description

Keywords

51 Physical Sciences, 5104 Condensed Matter Physics

Journal Title

Solid State Nuclear Magnetic Resonance

Conference Name

Journal ISSN

1527-3326
1527-3326

Volume Title

Publisher

Elsevier Inc.
Sponsorship
US Department of Energy (via State University of New York at Binghamton) (68799)
Oppenheimer Foundation. NECCES, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award No. DE-SC0012583. Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility Scientific Data and Computing Center, a component of the Computational Science Initiative, at Brookhaven National Laboratory, under Contract No. DE-SC0012704