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Title
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Topochemical nitridation with anion vacancy -assisted exchange
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Author
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Abstract
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| 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. |
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Language
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English
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Source (journal)
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Journal of the American Chemical Society. - Washington, D.C., 1879, currens
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Publication
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Washington, D.C.
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American Chemical Society
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2016
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ISSN
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0002-7863
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DOI
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10.1021/JACS.6B00088
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Volume/pages
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138
:9
(2016)
, p. 3211-3217
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ISI
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000371945800055
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Pubmed ID
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26855196
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Full text (Publisher's DOI)
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Full text (publisher's version - intranet only)
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