遷移金属含有エレクトライドを用いた非担持型触媒の開発

• Project/Area Number: 18J00745
• Research Category: Grant-in-Aid for JSPS Fellows
• Allocation Type: Single-year Grants
• Section: 国内
• Research Field: Functional solid state chemistry
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: 魯 楊帆 東京工業大学, 元素戦略研究センター, 特別研究員(PD)
• Project Period (FY): 2018-04-25 – 2021-03-31
• Project Status: Completed (Fiscal Year 2020)
• Budget Amount: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000); Fiscal Year 2020: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2019: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2018: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
• Keywords: エレクトライド / 鈴木カップリング反応 / パラジウム / ナノ化 / 金属間化合物 / アンモニア合成触媒 / 選択的水素化反応触媒 / モット絶縁体

Outline of Annual Research Achievements

一般的な不均一系触媒は遷移金属などの活性種と酸化物などの担体によって構成される。担体はPd等の貴金属を分散させる役割を持つものの、一般に担体と活性種の相互作用は弱く、触媒サイクルに寄与しない。一方、近年当グループが報告したRu/C12A7:e-等の触媒は担体が電子供与や水素吸蔵を通して触媒活性を大きく向上し、担体のアクティブな効果の重要性が認識されつつある。
申請者は触媒サイクルにおける担体の効果に着目し材料設計を行いNi/LaNとPd-ZrCを開発し、アンモニア合成及び鈴木カップリング等の重要な触媒反応で顕著な成果を挙げた。Ni/LaN触媒においてNiとLaNのそれぞれ異なる機能に着眼し、アンモニア合成において窒素と水素の活性化を空間的に分離することを着想した。本触媒においてLaNは窒素の吸収・活性化に寄与する一方Ni上では水素の開裂が進行し、その界面でアンモニアが発生する。この機構は「双活性点モデル」として今後の廉価なアンモニア触媒開発の重要な指標になるものと期待される。またPd-ZrC触媒では高表面積ZrC上でZrPd3を分散させることに成功した。本触媒では高価なPdの担持量を大きく低減できるだけでなく、ZrCからZrPd3へ電子供与がなされ、より低温で鈴木カップリング反応が進行することから産業界への応用が強く期待される。
以上の成果は活性種と担体を組み合わせこれまでにない機能を実現したものであり、不均一系触媒の材料設計において大きなインパクトを与えている。また、申請者は上記の内容を基に論文執筆知的財産構築にも貢献しており、期待以上の成果があったと評価できる。

Research Progress Status

令和2年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和2年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] マックスプランク研究所(ドイツ)
• [Int'l Joint Research] 華中科技大学(中国)
• [Int'l Joint Research] 中国科学院(中国)
• [Int'l Joint Research] マックスプランク研究所(ドイツ)
• [Int'l Joint Research] University of Wisconsin-Madison(米国)
• [Journal Article] Detecting electron-phonon coupling during photoinduced phase transition (2021)
  • Author(s): Suzuki Takeshi、Shinohara Yasushi、Lu Yangfan、Watanabe Mari、Xu Jiadi、Ishikawa Kenichi L.、Takagi Hide、Nohara Minoru、Katayama Naoyuki、Sawa Hiroshi、Fujisawa Masami、Kanai Teruto、Itatani Jiro、Mizokawa Takashi、Shin Shik、Okazaki Kozo
  • Journal Title: Physical Review B Volume: 103 Issue: 12 Pages: 1-10
  • DOI: 10.1103/physrevb.103.l121105
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Toward 2D Magnets in the (MnBi2Te4)(Bi2Te3)n Bulk Crystal (2020)
  • Author(s): Wu Jiazhen、Liu Fucai、Liu Can、Wang Yong、Li Changcun、Lu Yangfan、Matsuishi Satoru、Hosono Hideo
  • Journal Title: Advanced Materials Volume: 32 Issue: 23 Pages: 2001815-2001815
  • DOI: 10.1002/adma.202001815
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Anomalous Charge State Evolution and Its Control of Superconductivity in M3Al2C (M = Mo, W) (2020)
  • Author(s): Ying Tianping、Muraba Yoshinori、Iimura Soshi、Yu Tongxu、Cheng Peihong、Kamiya Toshio、Lu Yangfan、Li Jiang、Qi Yanpeng、Hosono Hideo
  • Journal Title: iScience Volume: 23 Issue: 6 Pages: 101196-101196
  • DOI: 10.1016/j.isci.2020.101196
  • Peer Reviewed
• [Journal Article] Vacancy-enabled N2 activation for ammonia synthesis on an Ni-loaded catalyst (2020)
  • Author(s): Ye Tian-Nan、Park Sang-Won、Lu Yangfan、Li Jiang、Sasase Masato、Kitano Masaaki、Tada Tomofumi、Hosono Hideo
  • Journal Title: Nature Volume: 583 Issue: 7816 Pages: 391-395
  • DOI: 10.1038/s41586-020-2464-9
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Resistive anisotropy of candidate excitonic insulator Ta2NiSe5 under pressure (2020)
  • Author(s): H. Arima, Y. Naito, K. Kudo, N. Katayama, H. Sawa, M. Nohara, Y. F. Lu, K. Kitagawa, H. Takagi, Y. Uwatoko and K. Matsubayashi
  • Journal Title: J. Phys Volume: 1609 Issue: 1 Pages: 012001-012001
  • DOI: 10.1088/1742-6596/1609/1/012001
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Contribution of Nitrogen Vacancies to Ammonia Synthesis over Metal Nitride Catalysts (2020)
  • Author(s): Ye Tian-Nan、Park Sang-Won、Lu Yangfan、Li Jiang、Sasase Masato、Kitano Masaaki、Hosono Hideo
  • Journal Title: Journal of the American Chemical Society Volume: 142 Issue: 33 Pages: 14374-14383
  • DOI: 10.1021/jacs.0c06624
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Intermetallic ZrPd3-Embedded Nanoporous ZrC as an Efficient and Stable Catalyst of the Suzuki Cross-Coupling Reaction (2020)
  • Author(s): Lu Yangfan、Ye Tian-Nan、Park Sang-Won、Li Jiang、Sasase Masato、Abe Hitoshi、Niwa Yasuhiro、Kitano Masaaki、Hosono Hideo
  • Journal Title: ACS Catalysis Volume: 10 Issue: 24 Pages: 14366-14374
  • DOI: 10.1021/acscatal.0c03416
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Efficient Ammonia Synthesis over Phase-Separated Nickel-Based Intermetallic Catalysts (2020)
  • Author(s): Ye Tian-Nan、Lu Yangfan、Kobayashi Yasukazu、Li Jiang、Park Sang-Won、Sasase Masato、Kitano Masaaki、Hosono Hideo
  • Journal Title: The Journal of Physical Chemistry C Volume: 124 Issue: 52 Pages: 28589-28595
  • DOI: 10.1021/acs.jpcc.0c09590
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Pseudogap Control of Physical and Chemical Properties in CeFeSi-Type Intermetallics (2019)
  • Author(s): Wu Jiazhen、Lu Erdong、Li Jiang、Lu Yangfan、Kitano Masaaki、Fredrickson Daniel C.、Inoshita Takeshi、Hosono Hideo
  • Journal Title: Inorganic Chemistry Volume: 58 Issue: 4 Pages: 2848-2855
  • DOI: 10.1021/acs.inorgchem.8b03539
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Palladium-bearing intermetallic electride as an?efficient and stable catalyst for Suzuki cross-coupling reactions (2019)
  • Author(s): Ye Tian-Nan、Lu Yangfan、Xiao Zewen、Li Jiang、Nakao Takuya、Abe Hitoshi、Niwa Yasuhiro、Kitano Masaaki、Tada Tomofumi、Hosono Hideo
  • Journal Title: Nature Communications Volume: 10 Issue: 1 Pages: 1-10
  • DOI: 10.1038/s41467-019-13679-0
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Valence-bond insulator in proximity to excitonic instability (2019)
  • Author(s): Y. Chiba, T. Mitsuoka, N. L. Saini, K. Horiba, M. Kobayashi, K. Ono, H. Kumigashira, N. Katayama, H. Sawa, M. Nohara, Y. F. Lu, H. Takagi, T. Mizokawa
  • Journal Title: Physical Review B Volume: 100 Issue: 24 Pages: 245129-245129
  • DOI: 10.1103/physrevb.100.245129
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Coherent order parameter oscillations in the ground state of the excitonic insulator Ta2NiSe5 (2018)
  • Author(s): Werdehausen Daniel、Takayama Tomohiro、Hoppner Marc、Albrecht Gelon、Rost Andreas W.、Lu Yangfan、Manske Dirk、Takagi Hidenori、Kaiser Stefan
  • Journal Title: Science Advances Volume: 4 Issue: 3 Pages: 8652-8652
  • DOI: 10.1126/sciadv.aap8652
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Photo-excited dynamics in the excitonic insulator Ta2NiSe5 (2018)
  • Author(s): Werdehausen Daniel、Takayama Tomohiro、Albrecht Gelon、Lu Yangfan、Takagi Hidenori、Kaiser Stefan
  • Journal Title: Journal of Physics: Condensed Matter Volume: 30 Issue: 30 Pages: 305602-305602
  • DOI: 10.1088/1361-648x/aacd76
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Realization of Mott-insulating electrides in dimorphic Yb5Sb3 (2018)
  • Author(s): Lu Yangfan、Wang Junjie、Li Jiang、Wu Jiazhen、Kanno Shu、Tada Tomofumi、Hosono Hideo
  • Journal Title: Physical Review B Volume: 98 Issue: 12 Pages: 125128-12540
  • DOI: 10.1103/physrevb.98.125128
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Photo-induced semimetallic states realised in electron-hole coupled insulators (2018)
  • Author(s): Kozo Okazaki, Yu Ogawa, Takeshi Suzuki, Takashi Yamamoto, Takashi Someya, Shoya Michimae, Mari Watanabe, Yangfan Lu, Minoru Nohara, Hidenori Takagi, Naoyuki Katayama, Hiroshi Sawa, Masami Fujisawa, Teruto Kanai, Nobuhisa Ishii, Jiro Itatani, Takashi Mizokawa, Shik Shin
  • Journal Title: Nature Communications Volume: 9:4322 Issue: 1 Pages: 1-6
  • DOI: 10.1038/s41467-018-06801-1
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Synthesis of Rare-Earth-Based Metallic Electride Nanoparticles and Their Catalytic Applications to Selective Hydrogenation and Ammonia Synthesis (2018)
  • Author(s): Lu Yangfan、Li Jiang、Ye Tian-Nan、Kobayashi Yasukazu、Sasase Masato、Kitano Masaaki、Hosono Hideo
  • Journal Title: ACS Catalysis Volume: 8 Issue: 12 Pages: 11054-11058
  • DOI: 10.1021/acscatal.8b03743
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Identifying quasi-2D and 1D electrides in yttrium and scandium chlorides via geometrical identification (2018)
  • Author(s): Wan Biao、Lu Yangfan、Xiao Zewen、Muraba Yoshinori、Kim Junghwan、Huang Dajian、Wu Lailei、Gou Huiyang、Zhang Jingwu、Gao Faming、Mao Ho-kwang、Hosono Hideo
  • Journal Title: npj Computational Materials Volume: 4 Issue: 1 Pages: 77-86
  • DOI: 10.1038/s41524-018-0136-1
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Presentation] Honeycomb lattice based electrides: Electronic structures and catalytic applications towards selective hydrogenation (2019)
  • Author(s): Y. F. Lu
  • Organizer: Material Research Meeting 2019
  • Int'l Joint Research
• [Patent(Industrial Property Rights)] 金属間化合物担持炭化ジルコニウム (2020)
  • Inventor(s): 細野秀雄、北野政明、魯楊帆、叶天南、横山壽治
  • Industrial Property Rights Holder: 細野秀雄、北野政明、魯楊帆、叶天南、横山壽治
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2020-081143
  • Filing Date: 2020
• [Patent(Industrial Property Rights)] 特許権 (2018)
  • Inventor(s): 細野秀雄、北野政明、多田朋史、横山壽治、戸田喜丈、魯楊帆、李江
  • Industrial Property Rights Holder: 東京工業大学、国立研究開発法人 科学技術振興機構
  • Industrial Property Rights Type: 特許
  • Filing Date: 2018
  • Acquisition Date: 2018
  • Overseas