A labile hydride strategy for the synthesis of heavily nitridized BaTiO3

Takeshi Yajima, Fumitaka Takeiri, Kohei Aidzu, Hirofumi Akamatsu, Koji Fujita, Wataru Yoshimune, Masatoshi Ohkura, Shiming Lei, Venkatraman Gopalan, Katsuhisa Tanaka, Craig M. Brown, Mark A. Green, Takafumi Yamamoto, Yoji Kobayashi, Hiroshi Kageyama

Research output: Contribution to journalArticle

50 Citations (Scopus)

Abstract

Oxynitrides have been explored extensively in the past decade because of their interesting properties, such as visible-light absorption, photocatalytic activity and high dielectric permittivity. Their synthesis typically requires high-temperature NH3 treatment (800-1,300 °C) of precursors, such as oxides, but the highly reducing conditions and the low mobility of N3- species in the lattice place significant constraints on the composition and structure-and hence the properties-of the resulting oxynitrides. Here we show a topochemical route that enables the preparation of an oxynitride at low temperatures (<500 °C), using a perovskite oxyhydride as a host. The lability of H-in BaTiO3-xHx (x ≤ 0.6) allows H-/N3- exchange to occur, and yields a room-temperature ferroelectric BaTiO3-xN2x/3. This anion exchange is accompanied by a metal-to-insulator crossover via mixed O-H-N intermediates. These findings suggest that this 'labile hydride' strategy can be used to explore various oxynitrides, and perhaps other mixed anionic compounds.

Original languageEnglish (US)
Pages (from-to)1017-1023
Number of pages7
JournalNature Chemistry
Volume7
Issue number12
DOIs
StatePublished - Dec 1 2015

Fingerprint

Hydrides
Perovskite
Temperature
Oxides
Light absorption
Ferroelectric materials
Anions
Ion exchange
Permittivity
Negative ions
Metals
Chemical analysis
perovskite

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Yajima, T., Takeiri, F., Aidzu, K., Akamatsu, H., Fujita, K., Yoshimune, W., ... Kageyama, H. (2015). A labile hydride strategy for the synthesis of heavily nitridized BaTiO3. Nature Chemistry, 7(12), 1017-1023. https://doi.org/10.1038/nchem.2370
Yajima, Takeshi ; Takeiri, Fumitaka ; Aidzu, Kohei ; Akamatsu, Hirofumi ; Fujita, Koji ; Yoshimune, Wataru ; Ohkura, Masatoshi ; Lei, Shiming ; Gopalan, Venkatraman ; Tanaka, Katsuhisa ; Brown, Craig M. ; Green, Mark A. ; Yamamoto, Takafumi ; Kobayashi, Yoji ; Kageyama, Hiroshi. / A labile hydride strategy for the synthesis of heavily nitridized BaTiO3. In: Nature Chemistry. 2015 ; Vol. 7, No. 12. pp. 1017-1023.
@article{65c54427a68142e68fee41459e15e47d,
title = "A labile hydride strategy for the synthesis of heavily nitridized BaTiO3",
abstract = "Oxynitrides have been explored extensively in the past decade because of their interesting properties, such as visible-light absorption, photocatalytic activity and high dielectric permittivity. Their synthesis typically requires high-temperature NH3 treatment (800-1,300 °C) of precursors, such as oxides, but the highly reducing conditions and the low mobility of N3- species in the lattice place significant constraints on the composition and structure-and hence the properties-of the resulting oxynitrides. Here we show a topochemical route that enables the preparation of an oxynitride at low temperatures (<500 °C), using a perovskite oxyhydride as a host. The lability of H-in BaTiO3-xHx (x ≤ 0.6) allows H-/N3- exchange to occur, and yields a room-temperature ferroelectric BaTiO3-xN2x/3. This anion exchange is accompanied by a metal-to-insulator crossover via mixed O-H-N intermediates. These findings suggest that this 'labile hydride' strategy can be used to explore various oxynitrides, and perhaps other mixed anionic compounds.",
author = "Takeshi Yajima and Fumitaka Takeiri and Kohei Aidzu and Hirofumi Akamatsu and Koji Fujita and Wataru Yoshimune and Masatoshi Ohkura and Shiming Lei and Venkatraman Gopalan and Katsuhisa Tanaka and Brown, {Craig M.} and Green, {Mark A.} and Takafumi Yamamoto and Yoji Kobayashi and Hiroshi Kageyama",
year = "2015",
month = "12",
day = "1",
doi = "10.1038/nchem.2370",
language = "English (US)",
volume = "7",
pages = "1017--1023",
journal = "Nature Chemistry",
issn = "1755-4330",
publisher = "Nature Publishing Group",
number = "12",

}

Yajima, T, Takeiri, F, Aidzu, K, Akamatsu, H, Fujita, K, Yoshimune, W, Ohkura, M, Lei, S, Gopalan, V, Tanaka, K, Brown, CM, Green, MA, Yamamoto, T, Kobayashi, Y & Kageyama, H 2015, 'A labile hydride strategy for the synthesis of heavily nitridized BaTiO3', Nature Chemistry, vol. 7, no. 12, pp. 1017-1023. https://doi.org/10.1038/nchem.2370

A labile hydride strategy for the synthesis of heavily nitridized BaTiO3. / Yajima, Takeshi; Takeiri, Fumitaka; Aidzu, Kohei; Akamatsu, Hirofumi; Fujita, Koji; Yoshimune, Wataru; Ohkura, Masatoshi; Lei, Shiming; Gopalan, Venkatraman; Tanaka, Katsuhisa; Brown, Craig M.; Green, Mark A.; Yamamoto, Takafumi; Kobayashi, Yoji; Kageyama, Hiroshi.

In: Nature Chemistry, Vol. 7, No. 12, 01.12.2015, p. 1017-1023.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A labile hydride strategy for the synthesis of heavily nitridized BaTiO3

AU - Yajima, Takeshi

AU - Takeiri, Fumitaka

AU - Aidzu, Kohei

AU - Akamatsu, Hirofumi

AU - Fujita, Koji

AU - Yoshimune, Wataru

AU - Ohkura, Masatoshi

AU - Lei, Shiming

AU - Gopalan, Venkatraman

AU - Tanaka, Katsuhisa

AU - Brown, Craig M.

AU - Green, Mark A.

AU - Yamamoto, Takafumi

AU - Kobayashi, Yoji

AU - Kageyama, Hiroshi

PY - 2015/12/1

Y1 - 2015/12/1

N2 - Oxynitrides have been explored extensively in the past decade because of their interesting properties, such as visible-light absorption, photocatalytic activity and high dielectric permittivity. Their synthesis typically requires high-temperature NH3 treatment (800-1,300 °C) of precursors, such as oxides, but the highly reducing conditions and the low mobility of N3- species in the lattice place significant constraints on the composition and structure-and hence the properties-of the resulting oxynitrides. Here we show a topochemical route that enables the preparation of an oxynitride at low temperatures (<500 °C), using a perovskite oxyhydride as a host. The lability of H-in BaTiO3-xHx (x ≤ 0.6) allows H-/N3- exchange to occur, and yields a room-temperature ferroelectric BaTiO3-xN2x/3. This anion exchange is accompanied by a metal-to-insulator crossover via mixed O-H-N intermediates. These findings suggest that this 'labile hydride' strategy can be used to explore various oxynitrides, and perhaps other mixed anionic compounds.

AB - Oxynitrides have been explored extensively in the past decade because of their interesting properties, such as visible-light absorption, photocatalytic activity and high dielectric permittivity. Their synthesis typically requires high-temperature NH3 treatment (800-1,300 °C) of precursors, such as oxides, but the highly reducing conditions and the low mobility of N3- species in the lattice place significant constraints on the composition and structure-and hence the properties-of the resulting oxynitrides. Here we show a topochemical route that enables the preparation of an oxynitride at low temperatures (<500 °C), using a perovskite oxyhydride as a host. The lability of H-in BaTiO3-xHx (x ≤ 0.6) allows H-/N3- exchange to occur, and yields a room-temperature ferroelectric BaTiO3-xN2x/3. This anion exchange is accompanied by a metal-to-insulator crossover via mixed O-H-N intermediates. These findings suggest that this 'labile hydride' strategy can be used to explore various oxynitrides, and perhaps other mixed anionic compounds.

UR - http://www.scopus.com/inward/record.url?scp=84947724100&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84947724100&partnerID=8YFLogxK

U2 - 10.1038/nchem.2370

DO - 10.1038/nchem.2370

M3 - Article

C2 - 26587718

AN - SCOPUS:84947724100

VL - 7

SP - 1017

EP - 1023

JO - Nature Chemistry

JF - Nature Chemistry

SN - 1755-4330

IS - 12

ER -

Yajima T, Takeiri F, Aidzu K, Akamatsu H, Fujita K, Yoshimune W et al. A labile hydride strategy for the synthesis of heavily nitridized BaTiO3. Nature Chemistry. 2015 Dec 1;7(12):1017-1023. https://doi.org/10.1038/nchem.2370