Topochemical Nitridation with Anion Vacancy-Assisted N3-/O2- Exchange

Riho Mikita; Tomoko Aharen; Takafumi Yamamoto; Fumitaka Takeiri; Tang Ya; Wataru Yoshimune; Koji Fujita; Suguru Yoshida; Katsuhisa Tanaka; Dmitry Batuk; Artem M. Abakumov; Craig M. Brown; Yoji Kobayashi; Hiroshi Kageyama

doi:10.1021/jacs.6b00088

Topochemical Nitridation with Anion Vacancy-Assisted N3-/O2- Exchange

Riho Mikita, Tomoko Aharen, Takafumi Yamamoto, Fumitaka Takeiri, Tang Ya, Wataru Yoshimune, Koji Fujita, Suguru Yoshida, Katsuhisa Tanaka, Dmitry Batuk, Artem M. Abakumov, Craig M. Brown, Yoji Kobayashi, Hiroshi Kageyama

Research output: Contribution to journal › Article › peer-review

43 Scopus citations

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 ∼ 0.18). At 400°C, similar to our studies on BaTiO3-xHx, hydride lability enables a low temperature direct ammonolysis of EuTi3.82+O2.82H0.18, leading to the N3-/H--exchanged product EuTi4+O2.82N0.12-0.06. When the ammonolysis temperature was increased up to 800°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 O2- only above 600°C and resulted in incomplete nitridation to EuTiO2.25N0.75, 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.

Original language	English (US)
Pages (from-to)	3211-3217
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	138
Issue number	9
DOIs	https://doi.org/10.1021/jacs.6b00088
State	Published - Mar 9 2016
Externally published	Yes

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Generated from Scopus record by KAUST IRTS on 2022-09-13

ASJC Scopus subject areas

Biochemistry
Colloid and Surface Chemistry
General Chemistry
Catalysis

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@article{15c51228b128439ead5d0f556216a72f,

title = "Topochemical Nitridation with Anion Vacancy-Assisted N3-/O2- Exchange",

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 ∼ 0.18). At 400°C, similar to our studies on BaTiO3-xHx, hydride lability enables a low temperature direct ammonolysis of EuTi3.82+O2.82H0.18, leading to the N3-/H--exchanged product EuTi4+O2.82N0.12-0.06. When the ammonolysis temperature was increased up to 800°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 O2- only above 600°C and resulted in incomplete nitridation to EuTiO2.25N0.75, 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.",

author = "Riho Mikita and Tomoko Aharen and Takafumi Yamamoto and Fumitaka Takeiri and Tang Ya and Wataru Yoshimune and Koji Fujita and Suguru Yoshida and Katsuhisa Tanaka and Dmitry Batuk and Abakumov, {Artem M.} and Brown, {Craig M.} and Yoji Kobayashi and Hiroshi Kageyama",

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year = "2016",

month = mar,

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doi = "10.1021/jacs.6b00088",

language = "English (US)",

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T1 - Topochemical Nitridation with Anion Vacancy-Assisted N3-/O2- Exchange

AU - Mikita, Riho

AU - Aharen, Tomoko

AU - Yamamoto, Takafumi

AU - Takeiri, Fumitaka

AU - Ya, Tang

AU - Yoshimune, Wataru

AU - Fujita, Koji

AU - Yoshida, Suguru

AU - Tanaka, Katsuhisa

AU - Batuk, Dmitry

AU - Abakumov, Artem M.

AU - Brown, Craig M.

AU - Kobayashi, Yoji

AU - Kageyama, Hiroshi

N1 - Generated from Scopus record by KAUST IRTS on 2022-09-13

PY - 2016/3/9

Y1 - 2016/3/9

N2 - 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 ∼ 0.18). At 400°C, similar to our studies on BaTiO3-xHx, hydride lability enables a low temperature direct ammonolysis of EuTi3.82+O2.82H0.18, leading to the N3-/H--exchanged product EuTi4+O2.82N0.12-0.06. When the ammonolysis temperature was increased up to 800°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 O2- only above 600°C and resulted in incomplete nitridation to EuTiO2.25N0.75, 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.

AB - 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 ∼ 0.18). At 400°C, similar to our studies on BaTiO3-xHx, hydride lability enables a low temperature direct ammonolysis of EuTi3.82+O2.82H0.18, leading to the N3-/H--exchanged product EuTi4+O2.82N0.12-0.06. When the ammonolysis temperature was increased up to 800°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 O2- only above 600°C and resulted in incomplete nitridation to EuTiO2.25N0.75, 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.

UR - https://pubs.acs.org/doi/10.1021/jacs.6b00088

UR - http://www.scopus.com/inward/record.url?scp=84960335784&partnerID=8YFLogxK

U2 - 10.1021/jacs.6b00088

DO - 10.1021/jacs.6b00088

M3 - Article

SN - 1520-5126

VL - 138

SP - 3211

EP - 3217

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 9

ER -

Topochemical Nitridation with Anion Vacancy-Assisted N3-/O2- Exchange

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