Glassy Distribution of Bi3+/Bi5+ in Bi1-xPbxNiO3 and Negative Thermal Expansion Induced by Intermetallic Charge Transfer

Kiho Nakano; Kengo Oka; Tetsu Watanuki; Masaichiro Mizumaki; Akihiko Machida; Akane Agui; Hyunjeong Kim; Jun Komiyama; Takashi Mizokawa; Takumi Nishikubo; Yuichiro Hattori; Shigenori Ueda; Yuki Sakai; Masaki Azuma

doi:10.1021/acs.chemmater.6b01160

Glassy Distribution of Bi³⁺/Bi⁵⁺ in Bi_1-xPb_xNiO₃ and Negative Thermal Expansion Induced by Intermetallic Charge Transfer

Kiho Nakano, Kengo Oka, Tetsu Watanuki, Masaichiro Mizumaki, Akihiko Machida, Akane Agui, Hyunjeong Kim, Jun Komiyama, Takashi Mizokawa, Takumi Nishikubo, Yuichiro Hattori, Shigenori Ueda, Yuki Sakai^*, Masaki Azuma

^*Corresponding author for this work

School of Advanced Science and Engineering

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

26 Citations (Scopus)

Abstract

The valence distribution and local structure of Bi_1-xPb_xNiO₃ (x ≤ 0.25) were investigated by comprehensive studies of Rietveld analysis of synchrotron X-ray diffraction (SXRD) data, X-ray absorption spectroscopy (XAS), hard X-ray photoemission spectroscopy (HAXPES), and pair distribution function (PDF) analysis of synchrotron X-ray total scattering data. Disproportionation of Bi ions into Bi³⁺ and Bi⁵⁺ was observed for all the samples, but it was a long-ranged one with distinct crystallographic sites in the P1 triclinic structure for x ≤ 0.15, while the ordering was short-ranged for x = 0.20 and 0.25. An intermetallic charge transfer between Bi⁵⁺ and Ni²⁺, leading to large volume shrinkage, was observed for all the samples upon heating at ∼500 K.

Original language	English
Pages (from-to)	6062-6067
Number of pages	6
Journal	Chemistry of Materials
Volume	28
Issue number	17
DOIs	https://doi.org/10.1021/acs.chemmater.6b01160
Publication status	Published - 2016 Sept 13

ASJC Scopus subject areas

Chemistry(all)
Chemical Engineering(all)
Materials Chemistry

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Nakano, K., Oka, K., Watanuki, T., Mizumaki, M., Machida, A., Agui, A., Kim, H., Komiyama, J., Mizokawa, T., Nishikubo, T., Hattori, Y., Ueda, S., Sakai, Y., & Azuma, M. (2016). Glassy Distribution of Bi³⁺/Bi⁵⁺ in Bi_1-xPb_xNiO₃ and Negative Thermal Expansion Induced by Intermetallic Charge Transfer. Chemistry of Materials, 28(17), 6062-6067. https://doi.org/10.1021/acs.chemmater.6b01160

Nakano, K, Oka, K, Watanuki, T, Mizumaki, M, Machida, A, Agui, A, Kim, H, Komiyama, J, Mizokawa, T, Nishikubo, T, Hattori, Y, Ueda, S, Sakai, Y & Azuma, M 2016, 'Glassy Distribution of Bi³⁺/Bi⁵⁺ in Bi_1-xPb_xNiO₃ and Negative Thermal Expansion Induced by Intermetallic Charge Transfer', Chemistry of Materials, vol. 28, no. 17, pp. 6062-6067. https://doi.org/10.1021/acs.chemmater.6b01160

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title = "Glassy Distribution of Bi3+/Bi5+ in Bi1-xPbxNiO3 and Negative Thermal Expansion Induced by Intermetallic Charge Transfer",

abstract = "The valence distribution and local structure of Bi1-xPbxNiO3 (x ≤ 0.25) were investigated by comprehensive studies of Rietveld analysis of synchrotron X-ray diffraction (SXRD) data, X-ray absorption spectroscopy (XAS), hard X-ray photoemission spectroscopy (HAXPES), and pair distribution function (PDF) analysis of synchrotron X-ray total scattering data. Disproportionation of Bi ions into Bi3+ and Bi5+ was observed for all the samples, but it was a long-ranged one with distinct crystallographic sites in the P1 triclinic structure for x ≤ 0.15, while the ordering was short-ranged for x = 0.20 and 0.25. An intermetallic charge transfer between Bi5+ and Ni2+, leading to large volume shrinkage, was observed for all the samples upon heating at ∼500 K.",

author = "Kiho Nakano and Kengo Oka and Tetsu Watanuki and Masaichiro Mizumaki and Akihiko Machida and Akane Agui and Hyunjeong Kim and Jun Komiyama and Takashi Mizokawa and Takumi Nishikubo and Yuichiro Hattori and Shigenori Ueda and Yuki Sakai and Masaki Azuma",

note = "Funding Information: This work was partially supported by KAKENHI on Innovative Areas (No. 26106507), 15K14119 and 16H02393, from the Japan Society for the Promotion of Science (JSPS), and by the Kanagawa Academy of Science and Technology (KAST).",

year = "2016",

month = sep,

day = "13",

doi = "10.1021/acs.chemmater.6b01160",

language = "English",

volume = "28",

pages = "6062--6067",

journal = "Chemistry of Materials",

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T1 - Glassy Distribution of Bi3+/Bi5+ in Bi1-xPbxNiO3 and Negative Thermal Expansion Induced by Intermetallic Charge Transfer

AU - Nakano, Kiho

AU - Oka, Kengo

AU - Watanuki, Tetsu

AU - Mizumaki, Masaichiro

AU - Machida, Akihiko

AU - Agui, Akane

AU - Kim, Hyunjeong

AU - Komiyama, Jun

AU - Mizokawa, Takashi

AU - Nishikubo, Takumi

AU - Hattori, Yuichiro

AU - Ueda, Shigenori

AU - Sakai, Yuki

AU - Azuma, Masaki

N1 - Funding Information: This work was partially supported by KAKENHI on Innovative Areas (No. 26106507), 15K14119 and 16H02393, from the Japan Society for the Promotion of Science (JSPS), and by the Kanagawa Academy of Science and Technology (KAST).

PY - 2016/9/13

Y1 - 2016/9/13

N2 - The valence distribution and local structure of Bi1-xPbxNiO3 (x ≤ 0.25) were investigated by comprehensive studies of Rietveld analysis of synchrotron X-ray diffraction (SXRD) data, X-ray absorption spectroscopy (XAS), hard X-ray photoemission spectroscopy (HAXPES), and pair distribution function (PDF) analysis of synchrotron X-ray total scattering data. Disproportionation of Bi ions into Bi3+ and Bi5+ was observed for all the samples, but it was a long-ranged one with distinct crystallographic sites in the P1 triclinic structure for x ≤ 0.15, while the ordering was short-ranged for x = 0.20 and 0.25. An intermetallic charge transfer between Bi5+ and Ni2+, leading to large volume shrinkage, was observed for all the samples upon heating at ∼500 K.

AB - The valence distribution and local structure of Bi1-xPbxNiO3 (x ≤ 0.25) were investigated by comprehensive studies of Rietveld analysis of synchrotron X-ray diffraction (SXRD) data, X-ray absorption spectroscopy (XAS), hard X-ray photoemission spectroscopy (HAXPES), and pair distribution function (PDF) analysis of synchrotron X-ray total scattering data. Disproportionation of Bi ions into Bi3+ and Bi5+ was observed for all the samples, but it was a long-ranged one with distinct crystallographic sites in the P1 triclinic structure for x ≤ 0.15, while the ordering was short-ranged for x = 0.20 and 0.25. An intermetallic charge transfer between Bi5+ and Ni2+, leading to large volume shrinkage, was observed for all the samples upon heating at ∼500 K.

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Glassy Distribution of Bi³⁺/Bi⁵⁺ in Bi_1-xPb_xNiO₃ and Negative Thermal Expansion Induced by Intermetallic Charge Transfer

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