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Probing Oxide-Ion Mobility in the Mixed Ionic-Electronic Conductor La$_2$NiO$_{4+δ}$ by Solid-State $^{17}$O MAS NMR Spectroscopy.

Published version
Peer-reviewed

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Authors

Halat, DM 
Dervişoğlu, R 
Dunstan, MT 
Blanc, F 

Abstract

While solid-state NMR spectroscopic techniques have helped clarify the local structure and dynamics of ionic conductors, similar studies of mixed ionic-electronic conductors (MIECs) have been hampered by the paramagnetic behavior of these systems. Here we report high-resolution 17O (I = 5/2) solid-state NMR spectra of the mixed-conducting solid oxide fuel cell (SOFC) cathode material La2NiO4+δ, a paramagnetic transition-metal oxide. Three distinct oxygen environments (equatorial, axial, and interstitial) can be assigned on the basis of hyperfine (Fermi contact) shifts and quadrupolar nutation behavior, aided by results from periodic DFT calculations. Distinct structural distortions among the axial sites, arising from the nonstoichiometric incorporation of interstitial oxygen, can be resolved by advanced magic angle turning and phase-adjusted sideband separation (MATPASS) NMR experiments. Finally, variable-temperature spectra reveal the onset of rapid interstitial oxide motion and exchange with axial sites at ∼130 °C, associated with the reported orthorhombic-to-tetragonal phase transition of La2NiO4+δ. From the variable-temperature spectra, we develop a model of oxide-ion dynamics on the spectral time scale that accounts for motional differences of all distinct oxygen sites. Though we treat La2NiO4+δ as a model system for a combined paramagnetic 17O NMR and DFT methodology, the approach presented herein should prove applicable to MIECs and other functionally important paramagnetic oxides.

Description

Keywords

0306 Physical Chemistry (incl. Structural), 0302 Inorganic Chemistry

Journal Title

Journal of the American Chemical Society

Conference Name

Journal ISSN

0002-7863
1520-5126

Volume Title

138

Publisher

American Chemical Society
Sponsorship
European Research Council (247411)
European Commission (275212)
Via membership of the U.K.’s HPC Materials Chemistry Consortium, some computations have made use of ARCHER, the U.K.’s national high-performance computing service, which is funded by the Office of Science and Technology through EPSRC’s High End Computing Programme (EPSRC Grant No. EP/L000202). This research also used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704. D.M.H. acknowledges funding from the Cambridge Commonwealth Trusts. C.P.G. and G.K. thank the European Research Council for an Advanced Fellowship [grant agreement No. 247411]. F.B. thanks the EU Marie Curie actions for an International Incoming Fellowship 2011−2013 (Grant 275212) and Clare Hall, University of Cambridge, for a Research Fellowship.