Development of hydrogenation and dehydrogenation catalysts using electride with hydrogen storage ability

• Project/Area Number: 15H04183
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Catalyst/Resource chemical process
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: Kitano Masaaki 東京工業大学, 元素戦略研究センター, 准教授 (50470117)
• Project Period (FY): 2015-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥17,940,000 (Direct Cost: ¥13,800,000、Indirect Cost: ¥4,140,000); Fiscal Year 2017: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000); Fiscal Year 2016: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000); Fiscal Year 2015: ¥10,660,000 (Direct Cost: ¥8,200,000、Indirect Cost: ¥2,460,000)
• Keywords: エレクトライド / 水素化物 / 選択水素化 / アンモニア合成 / ルテニウム / 触媒・化学プロセス / 水素化

Outline of Final Research Achievements

In the present study, we have focused on the hydrogenation or dehydrogenation reactions over electride (or hydride) supported metal nanoparticle catalysts. And the relationship between the catalytic activity and the hydrogen storage ability was investigated. C12A7 supported Ru-Fe bimetallic catalyst exhibited high activity for selective hydrogenation of unsaturated aldehydes. Ca2NH and Ca(NH2)2 supported Ru catalysts showed excellent activity for low-temperature ammonia synthesis.

Research Products

• [Journal Article] Self-organized Ruthenium-Barium Core-Shell Nanoparticles on a Mesoporous Calcium Amide Matrix for Efficient Low-Temperature Ammonia Synthesis (2018)
  • Author(s): Kitano Masaaki、Inoue Yasunori、Sasase Masato、Kishida Kazuhisa、Kobayashi Yasukazu、Nishiyama Kohei、Tada Tomofumi、Kawamura Shigeki、Yokoyama Toshiharu、Hara Michikazu、Hosono Hideo
  • Journal Title: Angewandte Chemie International Edition Volume: 57 Issue: 10 Pages: 2648-2652
  • DOI: 10.1002/anie.201712398
  • Peer Reviewed
• [Journal Article] Ternary intermetallic LaCoSi as a catalyst for N2 activation (2018)
  • Author(s): Gong Yutong、Wu Jiazhen、Kitano Masaaki、Wang Junjie、Ye Tian-Nan、Li Jiang、Kobayashi Yasukazu、Kishida Kazuhisa、Abe Hitoshi、Niwa Yasuhiro、Yang Hongsheng、Tada Tomofumi、Hosono Hideo
  • Journal Title: Nature Catalysis Volume: 1 Issue: 3 Pages: 178-185
  • DOI: 10.1038/s41929-017-0022-0
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Oblate hemispheroidal Large Ruthenium Particles Supported on Calcium Amide as Efficient Catalysts for Ammonia Decomposition (2018)
  • Author(s): Kishida Kazuhisa、Kitano Masaaki、Inoue Yasunori、Sasase Masato、Nakao Takuya、Tada Tomofumi、Abe Hitoshi、Niwa Yasuhiro、Yokoyama Toshiharu、Hara Michikazu、Hosono Hideo
  • Journal Title: Chemistry - A European Journal Volume: 印刷中 Issue: 31 Pages: 7976-7984
  • DOI: 10.1002/chem.201800467
  • Peer Reviewed
• [Journal Article] High Electron Density on Ru in Intermetallic YRu2: The Application to Catalyst for Ammonia Synthesis (2018)
  • Author(s): Takaya Ogawa, Yasukazu Kobayashi, Hiroshi Mizoguchi, Masaaki Kitano, Hitoshi Abe, Tomofumi Tada, Yoshitake Toda, Yasuhiro Niwa, Hideo Hosono
  • Journal Title: The Journal of Physical Chemistry C Volume: 印刷中
  • Peer Reviewed
• [Journal Article] Control of nitrogen activation ability by Co-Mo bimetallic nanoparticle catalysts prepared via sodium naphthalenide-reduction (2018)
  • Author(s): Yuki Tsuji, Kiya Ogasawara, Masaaki Kitano, Kazuhisa Kishida, Hitoshi Abe, Yasuhiro Niwa, Toshiharu Yokoyama, Michikazu Hara, Hideo Hosono
  • Journal Title: Journal of Catalysis Volume: 印刷中
  • Peer Reviewed
• [Journal Article] Tiered Electron Anions in Multiple Voids of LaScSi and Their Applications to Ammonia Synthesis (2017)
  • Author(s): Wu Jiazhen、Gong Yutong、Inoshita Takeshi、Fredrickson Daniel C.、Wang Junjie、Lu Yangfan、Kitano Masaaki、Hosono Hideo
  • Journal Title: Advanced Materials Volume: 29 Issue: 36 Pages: 1700924-1700924
  • DOI: 10.1002/adma.201700924
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Anchoring Bond between Ru and N Atoms of Ru/Ca2NH Catalyst: Crucial for the High Ammonia Synthesis Activity (2017)
  • Author(s): Abe Hitoshi、Niwa Yasuhiro、Kitano Masaaki、Inoue Yasunori、Sasase Masato、Nakao Takuya、Tada Tomofumi、Yokoyama Toshiharu、Hara Michikazu、Hosono Hideo
  • Journal Title: The Journal of Physical Chemistry C Volume: 121 Issue: 38 Pages: 20900-20904
  • DOI: 10.1021/acs.jpcc.7b07268
  • Peer Reviewed
• [Journal Article] Copper-Based Intermetallic Electride Catalyst for Chemoselective Hydrogenation Reactions (2017)
  • Author(s): Ye Tian-Nan、Lu Yangfan、Li Jiang、Nakao Takuya、Yang Hongsheng、Tada Tomofumi、Kitano Masaaki、Hosono Hideo
  • Journal Title: Journal of the American Chemical Society Volume: 139 Issue: 47 Pages: 17089-17097
  • DOI: 10.1021/jacs.7b08252
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Kinetic evidence: the rate-determining step for ammonia synthesis over electride-supported Ru catalysts is no longer the nitrogen dissociation step (2017)
  • Author(s): Yasukazu Kobayashi, Masaaki Kitano, Shigeki Kawamura, Toshiharu Yokoyama, Hideo Hosono
  • Journal Title: Catalysis Science & Technology Volume: 7 Issue: 1 Pages: 47-50
  • DOI: 10.1039/c6cy01962e
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Unique nanocages of 12CaO7Al2O3 boost heterolytic hydrogen activation and selective hydrogenation of heteroarenes over ruthenium catalyst (2017)
  • Author(s): Tian-Nan Ye, Jiang Li, Masaaki Kitano, Hideo Hosono
  • Journal Title: Green Chemistry Volume: 19 Issue: 3 Pages: 749-756
  • DOI: 10.1039/c6gc02782b
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Ru-Loaded C12A7:e-; Electride as a Catalyst for Ammonia Synthesis (2017)
  • Author(s): Michikazu Hara, Masaaki Kitano, Hideo Hosono
  • Journal Title: ACS Catalysis Volume: 7 Issue: 4 Pages: 2313-2324
  • DOI: 10.1021/acscatal.6b03357
  • Peer Reviewed
• [Journal Article] A chlorine-tolerant ruthenium catalyst derived from unique anion-exchange properties of 12CaO·7Al2O3 for ammonia synthesis (2017)
  • Author(s): Jiang Li, Masaaki Kitano, Tian-Nan Ye, Masato Sasase, Toshiharu Yokoyama, Hideo Hosono
  • Journal Title: ChemCatChem Volume: 印刷中 Issue: 15 Pages: 3078-3083
  • DOI: 10.1002/cctc.201700353
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Essential Role of Hydride Ion in Ruthenium-based Ammonia Synthesis Catalysts (2016)
  • Author(s): Masaaki Kitano, Yasunori Inoue, Hiroki Ishikawa, Kyosuke Yamagata, Takuya Nakao, Tomofumi Tada, Satoru Matsuishi, Toshiharu Yokoyama, Michikazu Hara, Hideo Hosono
  • Journal Title: Chemical Science Volume: 7 Issue: 7 Pages: 4036-4043
  • DOI: 10.1039/c6sc00767h
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Electronic interactions between a stable electride and a nano-alloy control the chemoselective reduction reaction (2016)
  • Author(s): Tian-Nan Ye, Jiang Li, Masaaki Kitano, Masato Sasase, Hideo Hosono
  • Journal Title: Chemical Science Volume: 7 Issue: 9 Pages: 5969-5975
  • DOI: 10.1039/c6sc01864e
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Hydride-Based Electride Material, LnH2 (Ln = La, Ce, or Y) (2016)
  • Author(s): Hiroshi Mizoguchi, Masaaki Okunaka, Masaaki Kitano, Satoru Matsuishi, Toshiharu Yokoyama, Hideo Hosono
  • Journal Title: Inorganic Chemistry Volume: 55 Issue: 17 Pages: 8833-8838
  • DOI: 10.1021/acs.inorgchem.6b01369
  • Peer Reviewed
• [Journal Article] The Key Indicator for the Control of Metal Particle Sizes on Supports from First Principles and Experimental Observation (2016)
  • Author(s): Takuya Nakao, Tomofumi Tada, Masaaki Kitano, Masato Sasase, Hideo Hosono
  • Journal Title: The Journal of Physical Chemistry C Volume: 120 Issue: 38 Pages: 21879-21887
  • DOI: 10.1021/acs.jpcc.6b03400
  • Peer Reviewed
• [Journal Article] Efficient and Stable Ammonia Synthesis by Self-Organized Flat Ru Nanoparticles on Calcium Amide (2016)
  • Author(s): Yasunori Inoue, Masaaki Kitano, Kazuhisa Kishida, Hitoshi Abe, Yasuhiro Niwa, Masato Sasase, Yusuke Fujita, Hiroki Ishikawa, Toshiharu Yokoyama, Michikazu Hara, Hideo Hosono
  • Journal Title: ACS Catalysis Volume: 6 Issue: 11 Pages: 7577-7584
  • DOI: 10.1021/acscatal.6b01940
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] エレクトライドによる触媒の電子状態制御 (2016)
  • Author(s): 北野政明
  • Journal Title: 科学と工業 Volume: 69-8 Pages: 676-677
• [Journal Article] 12CaO·7Al2O3エレクトライドの電子構造とアンモニア合成触媒としての応用 (2016)
  • Author(s): 北野政明
  • Journal Title: 触媒 Volume: 58 Pages: 198-201
• [Journal Article] チタン酸ナノチューブ固体酸およびエレクトライド担持ルテニウム触媒の開発 (2016)
  • Author(s): 北野政明
  • Journal Title: ペトロテック Volume: 39 Pages: 791-795
• [Journal Article] Water Durable Electride Y5Si3: Electronic Structure and Catalytic Activity for Ammonia Synthesis (2016)
  • Author(s): Yangfan Lu, Jiang Li, Tomofumi Tada, Yoshitake Toda, Shigenori Ueda, Toshiharu Yokoyama, Masaaki Kitano, Hideo Hosono
  • Journal Title: J. Am. Chem. Soc. Volume: 138 Issue: 12 Pages: 3970-3973
  • DOI: 10.1021/jacs.6b00124
  • Peer Reviewed
• [Journal Article] Mechanism Switching of Ammonia Synthesis Over Ru-loaded Electride Catalyst at Metal-Insulator Transition (2015)
  • Author(s): Shinji Kanbara, Masaaki Kitano, Yasunori Inoue, Toshiharu Yokoyama, Michikazu Hara, Hideo Hosono
  • Journal Title: J. Am. Chem. Soc. Volume: 137 Issue: 45 Pages: 14517-14524
  • DOI: 10.1021/jacs.5b10145
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Electron Donation Enhanced CO Oxidation over Ru-Loaded 12CaO7Al2O3 Electride Catalyst (2015)
  • Author(s): Md Jafar Sharif, Masaaki Kitano, Yasunori Inoue, Yasuhiro Niwa, Hitoshi Abe, Toshiharu Yokoyama, Michikazu Hara, Hideo Hosono
  • Journal Title: J. Phys. Chem. C Volume: 119 Issue: 21 Pages: 11725-11731
  • DOI: 10.1021/acs.jpcc.5b02342
  • Peer Reviewed
• [Presentation] Development of new solid catalysts containing high-density electrons or hydride ions for ammonia synthesis (2018)
  • Author(s): Masaaki Kitano
  • Organizer: Nankai University
  • Invited
• [Presentation] カルシウム窒化物を担体として利用した低温高活性アンモニア合成触媒 (2017)
  • Author(s): 北野政明
  • Organizer: 2016年度量子ビームサイエンスフェスタ
  • Place of Presentation: つくば国際会議場
  • Year and Date: 2017-03-14
  • Invited
• [Presentation] 低仕事関数材料による金属触媒の活性化 (2017)
  • Author(s): 北野政明
  • Organizer: 触媒学会界面分子変換研究会・日本表面科学会触媒表面科学研究部会合同ワークショップ, 「放談会：触媒研究の最前線と未来」
  • Place of Presentation: 東京大学
  • Year and Date: 2017-03-03
  • Invited
• [Presentation] Electride catalysts for ammonia synthesis and chemical reactions (2017)
  • Author(s): 北野政明
  • Organizer: The 1st International Symposium on Novel Materials for Next Generation Electronics and Catalysis
  • Place of Presentation: Tokyo Institute of Technology
  • Year and Date: 2017-02-17
  • Int'l Joint Research / Invited
• [Presentation] Application of inorganic electrides for ammonia synthesis (2017)
  • Author(s): 北野政明
  • Organizer: 第23回京都大学iCeMS国際シンポジウム
  • Invited
• [Presentation] 電子およびヒドリドイオンを含む担体を利用した低温アンモニア合成 (2017)
  • Author(s): 北野政明
  • Organizer: 工業触媒研究会研修会
  • Invited
• [Presentation] エレクトライドおよびハイドライドを利用した低温アンモニア合成 (2017)
  • Author(s): 北野政明
  • Organizer: 第２回固体化学フォーラム研究会
  • Invited
• [Presentation] 電子化物およびヒドリド化合物を触媒に利用した水素化反応 (2017)
  • Author(s): 北野政明
  • Organizer: 第55回触媒研究懇談会
  • Invited
• [Presentation] Ca-N-H系化合物を担体に利用した低温アンモニア合成 (2017)
  • Author(s): 北野政明
  • Organizer: 第120回触媒討論会
  • Invited
• [Presentation] エレクトライド触媒によるアンモニア合成の新技術－固体触媒からのアプローチ－ (2017)
  • Author(s): 北野政明
  • Organizer: 第7回化学フェスタ
  • Invited
• [Presentation] エレクトライドの電子物性と触媒特性 (2017)
  • Author(s): 北野政明
  • Organizer: 東工大元素戦略拠点シンポジウム
  • Invited
• [Presentation] 高活性アンモニア触媒Ru/Ca-N-H系化合物における水素の振る舞い (2017)
  • Author(s): 北野政明
  • Organizer: 第14回 水素量子アトミクス研究会
  • Invited
• [Presentation] エレクトライド触媒によるアンモニア合成における金属－担体相互作用 (2017)
  • Author(s): 北野政明
  • Organizer: 第31回日本放射光学会年会・放射光科学合同シンポジウム
  • Invited
• [Presentation] Ammonia synthesis over Ru-loaded Ca2NH: Effect H- ion on the catalytic performance (2017)
  • Author(s): Masaaki Kitano, Yasunori Inoue, Takuya Nakao, Tomofumi Tada, and Hideo Hosono
  • Organizer: 13th European Congress on Catalysis
  • Int'l Joint Research
• [Presentation] Ammonia synthesis over Co-Mo alloy catalyst prepared via sodium naphthalenide-driven reduction (2017)
  • Author(s): Yuki Tsuji, Masaaki Kitano, Kazuhisa Kishida, Masato Sasase, Toshiharu Yokoyama, Michikazu Hara, Hideo Hosono
  • Organizer: 13th European Congress on Catalysis
  • Int'l Joint Research
• [Presentation] Ammonia synthesis using inorganic electride catalysts (2016)
  • Author(s): 北野政明
  • Organizer: PCOSS-ICAT Joint International Symposium on Catalysis Science for Sustainable Society
  • Place of Presentation: Xiamen University, China
  • Year and Date: 2016-12-09
  • Int'l Joint Research / Invited
• [Presentation] 無機エレクトライドの電子供与能を利用した触媒反応 (2016)
  • Author(s): 北野政明
  • Organizer: 平成28年度触媒学会・触媒工業協会交流サロン
  • Place of Presentation: 化学会館
  • Year and Date: 2016-12-02
  • Invited
• [Presentation] Inorganic electride as a catalyst for ammonia synthesis (2016)
  • Author(s): 北野政明
  • Organizer: 第46回石油・石油化学討論会（京都大会）
  • Place of Presentation: 京都リサーチパーク
  • Year and Date: 2016-11-17
  • Invited
• [Presentation] 無機エレクトライド担持ルテニウム触媒の開発 (2016)
  • Author(s): 北野政明
  • Organizer: 第118回触媒討論会
  • Place of Presentation: 岩手大学
  • Year and Date: 2016-09-22
  • Invited
• [Presentation] 無機エレクトライド触媒によるアンモニア合成：電子およびヒドリドイオンの役割 (2016)
  • Author(s): 北野政明
  • Organizer: 日本セラミックス協会 第29回秋季シンポジウム
  • Place of Presentation: 広島大学
  • Year and Date: 2016-09-08
  • Invited
• [Presentation] Mechanism switching of ammonia synthesis over Ru-loaded 12CaO·7Al2O3 electride at metal-insulator transition (2016)
  • Author(s): Masaaki Kitano, Yasunori Inoue, Toshiharu Yokoyama, Michikazu Hara, Hideo Hosono
  • Organizer: The 16th International Congress on Catalysis
  • Place of Presentation: China National Convention Center, Beijing, China
  • Year and Date: 2016-07-05
  • Int'l Joint Research
• [Presentation] チタン酸ナノチューブ固体酸およびエレクトライド担持ルテニウム触媒に関する研究 (2016)
  • Author(s): 北野政明
  • Organizer: 石油学会第59回年会（第65回研究発表会）
  • Place of Presentation: タワーホール船堀
  • Year and Date: 2016-05-24
  • Invited
• [Presentation] 12CaO7Al2O3エレクトライドの電子特性を利用したアンモニア合成触媒 (2016)
  • Author(s): 北野政明
  • Organizer: 日本化学会 第96春季年会
  • Place of Presentation: 同志社大学(京都)
  • Year and Date: 2016-03-25
  • Invited
• [Presentation] 無機エレクトライドを利用したアンモニア合成 (2016)
  • Author(s): 北野政明
  • Organizer: 野口遵研究助成金講演会
  • Place of Presentation: 如水会館(東京)
  • Year and Date: 2016-03-11
  • Invited
• [Presentation] CO酸化反応における12CaO7Al2O3エレクトライドの電子供与効果 (2015)
  • Author(s): 北野政明・Sharif Jafar・井上泰徳・原亨和・細野秀雄
  • Organizer: 第31回ゼオライト研究発表会
  • Place of Presentation: とりぎん文化会館(鳥取)
  • Year and Date: 2015-11-26
• [Presentation] Ruthenium-Loaded 12CaO7Al2O3 Electride as a New Catalyst for Ammonia Synthesis (2015)
  • Author(s): Masaaki Kitano
  • Organizer: The 2nd Uppsala University-Tokyo Tech Joint Symposium
  • Place of Presentation: Tokyo Institute of technology（Tokyo)
  • Year and Date: 2015-11-16
  • Int'l Joint Research / Invited
• [Presentation] エレクトライドの触媒反応への応用 (2015)
  • Author(s): 北野政明
  • Organizer: 電子セラミックスプロセス研究会
  • Place of Presentation: 東京工業大学(神奈川)
  • Year and Date: 2015-05-30
  • Invited
• [Book] アンモニアを用いた水素エネルギーシステム (2015)
  • Author(s): 原亨和，北野政明，細野秀雄
  • Total Pages: 239
  • Publisher: シーエムシー出版
• [Remarks] 東京工業大学 減租戦略研究センター 北野研究室
  • URL: http://www.mces.titech.ac.jp/authors/kitano
• [Remarks] 東京工業大学 元素戦略研究センター 北野研究室
  • URL: http://www.mces.titech.ac.jp/authors/kitano/
• [Patent(Industrial Property Rights)] アンモニア合成用触媒の製造方法及びアンモニアの製造方法 (2017)
  • Inventor(s): 細野秀雄、北野政明、横山壽治、李江、河村重喜、岸田和久
  • Industrial Property Rights Holder: 細野秀雄、北野政明、横山壽治、李江、河村重喜、岸田和久
  • Industrial Property Rights Type: 特許
  • Filing Date: 2017
  • Overseas
• [Patent(Industrial Property Rights)] 金属間化合物、水素吸放出材料、触媒及びアンモニアの製造方法 (2017)
  • Inventor(s): 細野秀雄、北野政明、WU JIAZHEN、横山壽治
  • Industrial Property Rights Holder: 細野秀雄、北野政明、WU JIAZHEN、横山壽治
  • Industrial Property Rights Type: 特許
  • Filing Date: 2017
• [Patent(Industrial Property Rights)] 金属担持物、担持金属触媒、アンモニアの製造方法、水素の製造方法及びシアナミド化合物の製造方法 (2017)
  • Inventor(s): 細野秀雄、岸田和久、北野政明、横山壽治、
  • Industrial Property Rights Holder: 細野秀雄、岸田和久、北野政明、横山壽治、
  • Industrial Property Rights Type: 特許
  • Filing Date: 2017-03-17
• [Patent(Industrial Property Rights)] アンモニア合成用触媒の製造方法及びアンモニアの製造方法 (2016)
  • Inventor(s): 細野秀雄、北野政明、横山壽治、李江、河村重喜、岸田和久
  • Industrial Property Rights Holder: 細野秀雄、北野政明、横山壽治、李江、河村重喜、岸田和久
  • Industrial Property Rights Type: 特許
  • Filing Date: 2016-08-08
• [Patent(Industrial Property Rights)] ラーベス相金属間化合物、金属間化合物を用いた触媒、及びアンモニア製造方法 (2016)
  • Inventor(s): 細野秀雄、横山壽治、北野政明、溝口拓、小川敬也
  • Industrial Property Rights Holder: 細野秀雄、横山壽治、北野政明、溝口拓、小川敬也
  • Industrial Property Rights Type: 特許
  • Filing Date: 2016-09-15
  • Overseas
• [Patent(Industrial Property Rights)] 金属担持物、担持金属触媒及び該触媒を用いるアンモニア合成法 (2016)
  • Inventor(s): 細野秀雄、原亨和、北野政明、溝口拓、横山壽治、山縣 亨介
  • Industrial Property Rights Holder: 細野秀雄、原亨和、北野政明、溝口拓、横山壽治、山縣 亨介
  • Industrial Property Rights Type: 特許
  • Filing Date: 2016-11-09
  • Overseas
• [Patent(Industrial Property Rights)] 遷移金属担持金属間化合物、担持金属触媒、及びアンモニアの製造方法 (2016)
  • 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
  • Industrial Property Rights Holder: 細野秀雄、北野政明、多田朋史 、横山壽治, 戸田喜丈、魯楊帆
  • Industrial Property Rights Type: 特許
  • Filing Date: 2016-12-22
  • Overseas