Publication
Title
Topochemical nitridation with anion vacancy -assisted exchange
Author
Abstract
We present how the introduction of anion vacancies in oxyhydrides enables a route to access new oxynitrides, by conducting ammonolysis of perovskite oxyhydride EuTiO3-xHx (x similar to 0.18). At 400 degrees C, similar to our studies on BaTiO3-xHx, hydride lability enables a low temperature direct ammonolysis of EUTi3.82+O-2.82/H-0.18, leading to the N3-/H--exchanged product EuTi4+O2.82No0.12 square 0.06 center dot When the ammonolysis temperature was increased up to 800 degrees C, we observed a further nitridation involving N3-/O2- exchange, yielding a fully oxidized Eu3+Ti4+O2N with the GdFeO3-type distortion (Pnma) as a metastable phase, instead of pyrochlore structure. Interestingly, the same reactions using the oxide EuTiO3 proceeded through a 1:1 exchange of N3- with O-2 only above 600 degrees C and resulted in incomplete nitridation to EuTi02.25N0.75, indicating that anion vacancies created during the initial nitridation process of EuTiO2.82H0.18 play a crucial role in promoting anion (N3-/O2-) exchange at high temperatures. Hence, by using (hydride-induced) anion-deficient precursors, we should be able to expand the accessible anion composition of perovskite oxynitrides.
Language
English
Source (journal)
Journal of the American Chemical Society. - Washington, D.C.
Publication
Washington, D.C. : 2016
ISSN
0002-7863
Volume/pages
138:9(2016), p. 3211-3217
ISI
000371945800055
Full text (Publishers DOI)
Full text (publishers version - intranet only)
UAntwerpen
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Publication type
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Affiliation
Publications with a UAntwerp address
External links
Web of Science
Record
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Creation 10.05.2016
Last edited 17.05.2017
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