On the development of the rational method for crystal structure control and pioneering nanomaterials

• Project/Area Number: 18K14073
• Research Category: Grant-in-Aid for Early-Career Scientists
• Allocation Type: Multi-year Fund
• Review Section: Basic Section 28010:Nanometer-scale chemistry-related
• Research Institution: Kyoto University
• Principal Investigator: Kusada Kohei 京都大学, 理学研究科, 特定助教 (50741857)
• Project Period (FY): 2018-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2019: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2018: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
• Keywords: 金属ナノ粒子 / 触媒 / 結晶構造制御 / 結晶構造

Outline of Final Research Achievements

Within this study period, the crystal-structure control mechanism of the fcc structured Ru was experimentally elucidated using in-situ X-ray absorption spectroscopy and X-ray diffraction. Based on these results, we have succeeded in synthesizing for the first time Os nanoparticles with fcc structures, although Os normally form only hcp structure. This is a new example that the crystal structure of metal nanoparticles can be controlled by synthetic conditions, and it was shown that the "crystal structure" in this proposal can be a new degree of freedom. In the alloy system, we have also selectively fabricated PdRu solid solution alloys with fcc or hcp structure, and found that the change in crystal structure resulted in a significant difference in durability in electrochemical catalytic reactions.

Academic Significance and Societal Importance of the Research Achievements

本研究は、バルクでは存在しない結晶構造を有する金属ナノ粒子の合理的な設計指針を確立し、結晶構造制御が物性に与える影響を調べることを目的とした。これまで、金属ナノ粒子開発には粒径や結晶面の制御など精密な制御が行われている。しかし、これらは、古くから築き上げられた金属状態図の範疇にあり、未だ材料設計に制限がある。本研究で得られた成果の金属ナノ粒子の結晶構造制御による物性開拓は世界でも報告例がなく、学術的にも極めて独自性が高い。結晶構造は物質の電子状態・表面構造に密接に関係するものであり、得られた新規物室は既存の物質とは全く異なる電子状態および物性を有し、新材料の創造的な設計に活用が可能である 。

Research Products

• [Journal Article] Discovery of face-centred cubic Os nanoparticles (2020)
  • Author(s): Wakisaka Takuo、Kusada Kohei、Yamamoto Tomokazu、Toriyama Takaaki、Matsumura Syo、Ibrahima Gueye、Seo Okkyun、Kim Jaemyung、Hiroi Satoshi、Sakata Osami、Kawaguchi Shogo、Kubota Yoshiki、Kitagawa Hiroshi
  • Journal Title: Chemical Communications Volume: 56 Issue: 3 Pages: 372-374
  • DOI: 10.1039/c9cc09192k
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] New Aspects of Platinum Group Metal‐Based Solid‐Solution Alloy Nanoparticles: Binary to High‐Entropy Alloys (2020)
  • Author(s): Kusada Kohei、Wu Dongshuang、Kitagawa Hiroshi
  • Journal Title: Chemistry - A European Journal Volume: 26 Issue: 23 Pages: 5105-5130
  • DOI: 10.1002/chem.201903928
  • Peer Reviewed
• [Journal Article] NMR-based gap behavior related to the quantum size effect (2020)
  • Author(s): Okuno Tomonori、Manago Masahiro、Kitagawa Shunsaku、Ishida Kenji、Kusada Kohei、Kitagawa Hiroshi
  • Journal Title: Physical Review B Volume: 101 Issue: 12 Pages: 121406-121406
  • DOI: 10.1103/physrevb.101.121406
  • Peer Reviewed
• [Journal Article] Rational Synthesis for a Noble Metal Carbide (2019)
  • Author(s): W. Takuo, K. Kohei, W. Dongshuang, Y. Tomokazu, T. Takaaki, M. Syo, A. Hiroshi, Y. Osamu, I. Kazutaka, O. Toshiya, P. Natalia, C. Yanna, K. Loku S. R., S. Chulho, S. Osami, X. Wei, K. Michihisa, K. Yoshiki, K. Shogo, A. Ryan L., A. Susan M., A. Elvis F., N. Hiroshi, K. Hiroshi
  • Journal Title: Journal of the American Chemical Society Volume: 142 Issue: 3 Pages: 1247-1253
  • DOI: 10.1021/jacs.9b09219
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Investigation of selective chemisorption of fcc and hcp Ru nanoparticles using X-ray photoelectron spectroscopy analysis (2019)
  • Author(s): Gueye Ibrahima、Kim Jaemyung、Kumara L.S.R.、Yang Anli、Seo Okkyun、Chen Yanna、Song Chulho、Hiroi Satoshi、Kusada Kohei、Kobayashi Hirokazu、Kitagawa Hiroshi、Sakata Osami
  • Journal Title: Journal of Catalysis Volume: 380 Pages: 247-253
  • DOI: 10.1016/j.jcat.2019.10.004
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Hydrogen in Palladium and Storage Properties of Related Nanomaterials: Size, Shape, Alloying, and Metal‐Organic Framework Coating Effects (2019)
  • Author(s): Dekura Shun、Kobayashi Hirokazu、Kusada Kohei、Kitagawa Hiroshi
  • Journal Title: ChemPhysChem Volume: 20 Issue: 10 Pages: 1158-1176
  • DOI: 10.1002/cphc.201900109
  • Peer Reviewed
• [Journal Article] Emergence of high ORR activity through controlling local density-of-states by alloying immiscible Au and Ir (2019)
  • Author(s): Kusada Kohei、Wu Dongshuang、Yamamoto Tomokazu、Toriyama Takaaki、Matsumura Syo、Xie Wei、Koyama Michihisa、Kawaguchi Shogo、Kubota Yoshiki、Kitagawa Hiroshi
  • Journal Title: Chemical Science Volume: 10 Issue: 3 Pages: 652-656
  • DOI: 10.1039/c8sc04135k
  • Peer Reviewed / Open Access
• [Journal Article] Correlation between the electronic/local structure and CO-oxidation activity of PdxRu1-x alloy nanoparticles (2019)
  • Author(s): Song Chulho、Tayal Akhil、Seo Okkyun、Kim Jaemyung、Chen Yanna、Hiroi Satoshi、Kumara L. S. R.、Kusada Kohei、Kobayashi Hirokazu、Kitagawa Hiroshi、Sakata Osami
  • Journal Title: Nanoscale Advances Volume: 1 Issue: 2 Pages: 546-553
  • DOI: 10.1039/c8na00305j
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Size effects on rhodium nanoparticles related to hydrogen-storage capability (2018)
  • Author(s): Song Chulho、Yang Anli、Sakata Osami、Kumara L. S. R.、Hiroi Satoshi、Cui Yi-Tao、Kusada Kohei、Kobayashi Hirokazu、Kitagawa Hiroshi
  • Journal Title: Physical Chemistry Chemical Physics Volume: 20 Issue: 22 Pages: 15183-15191
  • DOI: 10.1039/c8cp01678j
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Crystal Structure-dependent Thermal Stability and Catalytic Performance of AuRu3 Solid-solution Alloy Nanoparticles (2018)
  • Author(s): Zhang Quan、Kusada Kohei、Wu Dongshuang、Kawaguchi Shogo、Kubota Yoshiki、Kitagawa Hiroshi
  • Journal Title: Chemistry Letters Volume: 47 Issue: 4 Pages: 559-561
  • DOI: 10.1246/cl.180047
  • NAID: 130006638876
  • Peer Reviewed
• [Presentation] Development of New Solid-Solution Alloy Nanoparticles for Catalytic Applications Based on Density-of-States Engineering (2019)
  • Author(s): Kohei Kusada, Dongshuang Wu, Tomokazu Yamamoto, Syo Matsumura, Wei Xie, Michihisa Koyama, Katsutoshi Sato, Katsutoshi Nagaoka and Hiroshi Kitagawa
  • Organizer: Okinawa Colloids 2019
  • Int'l Joint Research
• [Presentation] Development of New Solid-Solution Alloy Nanoparticles for Three-Way Catalytic Applications (2019)
  • Author(s): Kohei Kusada
  • Organizer: MRS Fall 2019
  • Int'l Joint Research
• [Presentation] Characterization and HER Catalytic Activity of Novel Rhodium Carbide (2019)
  • Author(s): Takuo Wakisaka, Kohei Kusada, Dongshuang Wu, Tomokazu Yamamoto, Syo Matsumura, Takaaki Toriyama, Wei Xie, Michihisa Koyama, Hiroshi Akiba, Osamu Yamamuro, Kazutaka Ikeda, Toshiya Otomo, Shogo Kawaguchi, Yoshiki Kubota, Hiroshi Kitagawa
  • Organizer: The 99th CSJ Annual Meeting
• [Presentation] Phase-Controlled Metal NPs for Catalytic Applications (2018)
  • Author(s): Kohei Kusada
  • Organizer: The 4th Korea-Japan Joint Symposium on Hydrogen in Materials
  • Int'l Joint Research
• [Presentation] Development of New Solid-Solution Alloy Nanoparticles for Catalytic Applications on the Basis of Density-of-States Engineering (2018)
  • Author(s): Kohei Kusada
  • Organizer: 2018 MRS Fall Meeting
  • Int'l Joint Research
• [Book] ハイエントロピー合金 (2020)
  • Author(s): 乾 晴行
  • Total Pages: 296
  • Publisher: 内田老鶴圃
  • ISBN: 9784753651375
• [Book] 現代化学 (2018)
  • Author(s): 草田康平、北川宏
  • Total Pages: 80
  • Publisher: 株式会社 東京化学同人
• [Patent(Industrial Property Rights)] 白金族多元系固溶体及びその製造方法並びに触媒及びその製造方法 (2019)
  • Inventor(s): 北川宏、草田康平、Dongshuang Wu
  • Industrial Property Rights Holder: 北川宏、草田康平、Dongshuang Wu
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2019-138940
  • Filing Date: 2019