Dinitrogen Reduction by Metal Complexes in Specific Ionic Liquid Reaction Field

• Project/Area Number: 24655048
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Single-year Grants
• Research Field: Inorganic chemistry
• Research Institution: Nagoya Institute of Technology
• Principal Investigator: MASUDA HIDEKI 名古屋工業大学, 工学(系)研究科(研究院), 教授 (50209441)
• Project Period (FY): 2012-04-01 – 2014-03-31
• Project Status: Completed (Fiscal Year 2013)
• Budget Amount: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2013: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000); Fiscal Year 2012: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: イオン液体 / 金属錯体 / 窒素固定化 / アンモニア / 空中窒素固定 / 電気化学的還元 / 錯体触媒 / アンモニア合成 / 電流効率 / 窒素捕捉 / 窒素の還元 / 電気化学

Research Abstract

Ammonia attracts attention as not only raw materials of manures and chemical products but also a next-generation energy source for the fossil fuel.We developed a new synthetic method of ammonia environmental-friendly as follows. We prepared the ammonia from dinitrogen gas and water-originated hydrogen in an ionic liquid electrochemically.

Research Products

• [Journal Article] Deprotonation/Protonation-Driven Change of The o-Donor Ability of a Sulfur Atom in Iron(II) Complexes with a Thioamide SNS Pincer Type Ligand (2014)
  • Author(s): T. Suzuki, Y. Kajita, and H. Masuda
  • Journal Title: Dalton Trans. Volume: (in press) Issue: 25 Pages: 9732-9739
  • DOI: 10.1039/c4dt00524d
  • Peer Reviewed / Open Access
• [Journal Article] Adsorption and Selective Detection of Microbes using a Au Substrate Modified with a Hydroxamate- and Catecholate-Type Artificial Siderophore-Fe3+ Complexes (2013)
  • Author(s): T. Inomata, H. Tanabashi, Y. Funahashi, T. Ozawa, H. Masuda
  • Journal Title: Dalton Transaction Volume: 42 Issue: 45 Pages: 16043-16048
  • DOI: 10.1039/c3dt51448j
  • Peer Reviewed
• [Journal Article] Enantioselective monofluoromethylation of aldehydes with 2-fluoro-1,3-benzodithiole-1,1,3,3-tetraoxide catalyzed by a bifunctional cinchona alkaloid-derived thiourea-titanium complex (2013)
  • Author(s): H. Ma, K. Matsuzaki, Y.-D. Yang, E. Tokunaga, D. Nakane, T. Ozawa, H. Masuda, N. Shibata
  • Journal Title: Chem. Comm. Volume: 49 Issue: 95 Pages: 11206-11208
  • DOI: 10.1039/c3cc46544f
  • Peer Reviewed
• [Journal Article] Superoxide disproportionation driven by zinc complexes with various steric and electrostatic properties (2013)
  • Author(s): Akira Wada, Koichiro Jitsukawa, Hideki Masuda
  • Journal Title: Angew Chem Int Ed. Volume: 52 Issue: 47 Pages: 12293-12293
  • DOI: 10.1002/anie.201305459
  • Peer Reviewed / Open Access
• [Journal Article] A Phosphonium-Type Ionic Liquid-Modified Au Electrode: A New Platform for Entrapping Functional Molecules on Substrate Surfaces (2013)
  • Author(s): T. Kitagawa, T. Inomata, Y. Funahashi, T, Ozawa, H. Masuda
  • Journal Title: Chemical Communications Volume: 49 Issue: 86 Pages: 10184-10186
  • DOI: 10.1039/c3cc45251d
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of Tricarbonyl- Molybdenum Complexes Bearing Monoaza- Trithia-Macrocyclic Ligands (2013)
  • Author(s): T. Ogawa, K. Koike, J. Matsumoto, Y. Kajita, and H. Masuda
  • Journal Title: Inorg. Chim. Acta Volume: 401 Pages: 101-106
  • DOI: 10.1016/j.ica.2013.03.027
• [Journal Article] Highly selective binding of nitric oxide by Co^<III> and Fe^<III> complexes (2013)
  • Author(s): Z. Zhang, T. Suwabe, M Ishikawa, Y. Funahashi, T. Inomata, T. Ozawa and H. Masuda
  • Journal Title: Dalton Trans. Volume: 42(13) Pages: 4470-4478
• [Journal Article] Preparation, Characterization, and Reactivity of Dinitrogen Molybdenum Complexes with Bis(diphenylphosphino) amine Derivative Ligands that Form a Unique 4-Membered P-N-P Chelate Ring (2013)
  • Author(s): T. Ogawa, Y. Kajita, Y. Wasada-Tsutsui, H. Wasada, and H. Masuda
  • Journal Title: Inorg. Chem. Volume: 52(1) Issue: 1 Pages: 182-195
  • DOI: 10.1021/ic301577a
• [Journal Article] Preparation, Characterization, and Reactivity of Dinitrogen Molybdenum Complexes with Bis(diphenylphosphino)amine Derivative Ligands that Form a Unique 4-Membered P-N-P Chelate Ring (2013)
  • Author(s): Takahiko Ogawa, Yuji Kajita, Yuko Wasada-Tsutsui, Hiroaki Wasada, and Hideki Masuda
  • Journal Title: Inorg. Chem., Volume: 52 Pages: 182-195
  • Peer Reviewed
• [Journal Article] Highly selective binding of nitric oxide by CoIII and FeIII complexes (2013)
  • Author(s): Zizheng Zhang, Tatsuya Suwabe, Mai Ishikawa, Yasuhiro Funahashi, Tomohiko Inomata, Tomohiro Ozawa and Hideki Masuda
  • Journal Title: Dalton Trans Volume: 42 Pages: 4470-4478
  • Peer Reviewed
• [Journal Article] Characterization and Application of Ru2+ Complex with Square-planar Quadridentate Ligand Conatining Arylamines for Dye-sensitized Solar Cells (2013)
  • Author(s): Tomohiko Inomata, Kousuke Yamamoto, Yasuhiro Funahashi, Tomohiro Ozawa, and Hideki Masuda
  • Journal Title: Jpn. J. Appl. Phys Volume: 52
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of Tricarbonyl-Molybdenum Complexes Bearing Monoaza-Trithia-Macrocyclic Ligands (2013)
  • Author(s): Takahiko Ogawa, Koji Koike, Jun Matsumoto, Yuji Kajita, and Hideki Masuda
  • Journal Title: Inorg. Chim. Acta Volume: 401 Pages: 101-106
  • Peer Reviewed
• [Journal Article] Catalytic Enantioselective Allylation of Ketimines by Using Palladium Pincer Complexes with Chiral Bis(imidazoline)s (2013)
  • Author(s): Shuichi Nakamura, Kengo Hyodo, Masayuki Nakamura, Daisuke Nakane, and Hideki Masuda
  • Journal Title: Chemistry - A European Journal Volume: 19 Pages: 7304-7309
  • Peer Reviewed
• [Journal Article] Trichlorido{methyl[4-(methylimino)pent-2-en-2-yl]azanido-κ2N,N'}hafnium(IV) (2013)
  • Author(s): Ken Ikeda and Hideki Masuda
  • Journal Title: Acta Cryst., Volume: E69
  • Peer Reviewed
• [Journal Article] Dichlorido[6,8,22,24,34,36-hexamethyl-33,35-diaza- 3,11,19,27-tetraazoniapenta- cyclo[27.3.1.15,9.113,17.121,25]hexatriaconta-(33),5,7,9(34),13,15,17(35),21,23,25(36),29,31-dodecaene-κ6N3,N11,N19,N27,N33,N35]dipalladium(II) bis(perchlorate) N,N -dimethylformamide disolvate methanol disolvate (2013)
  • Author(s): Kohei Oda, Yasuhiro Fnahashi and Hideki Masuda
  • Journal Title: Acta Cryst. Volume: E69
  • Peer Reviewed
• [Journal Article] A Phosphonium-type Ionic Liquid-modified Au Electrode: A New Platform for Entrapping Functional Molecules on Substrate Surfaces (2013)
  • Author(s): Tatsuya Kitagawa, Tomohiko Inomata, Yasuhiro Funahashi, Tomohiko Ozawa, and Hideki Masuda
  • Journal Title: Chem Commun. Volume: 49 Pages: 10184-10186
  • Peer Reviewed
• [Journal Article] Superoxide Disproportionation Driven by Zinc Complexes with Various Steric and Electrostatic Properties (2013)
  • Author(s): Akira Wada, Koichiro Jitsukawa and Hideki Masuda
  • Journal Title: Angew. Chem. Int. Ed Volume: 52 Pages: 12454-12459
  • Peer Reviewed
• [Journal Article] tereoselective Synthesis of Vinyl Triflones and Heteroaryl Triflones via Anionic O→Cvinyl/N→Cvinyl Trifluoromethanesulfonyl Migration Reactions (2013)
  • Author(s): Xiu-Hua Xu, Misaki Taniguchi, Xin Wang, Etsuko Tokunaga, Tomohiro Ozawa, Hideki Masuda, and Norio Shibata*
  • Journal Title: Angew. Chem. Int. Ed Volume: 52 Pages: 12628-12631
  • Peer Reviewed
• [Journal Article] Enantioselective monofluoromethylation of aldehydes with 2-fluoro-1,3-benzodithiole- 1,1,3,3-tetraoxide catalyzed by a bifunctional cinchona alkaloid-derived thiourea-titanium complex (2013)
  • Author(s): Hai Ma, Kohei Matsuzaki, Yu-Dong Yang, Etsuko Tokunaga, Daisuke Nakane, Tomohiro Ozawa, Hideki Masuda, and Norio Shibata
  • Journal Title: Chem. Commun. Volume: 49 Pages: 11206-11208
  • Peer Reviewed
• [Journal Article] Adsorption and Detection of Escherichia coli using an Au substrate modified with a catecholate-type artificial siderophore-Fe3+ complex (2013)
  • Author(s): omohiko Inomata, Hirohito Tanabashi, Yasuhiro Funahashi, Tomohiro Ozawa, and Hideki Masuda
  • Journal Title: Dalton Trans. Volume: 42 Pages: 16043-16048
  • Peer Reviewed
• [Journal Article] Preparation, Characterization, and Reactivity of Dinitrogen Molybdenum Complexes with Bis(diphenylphosphino)amine Derivative Ligands that Form a Unique 4-Membered P-N-P Chelate Ring (2012)
  • Author(s): Takahiko Ogawa, Yuji Kajita, Yuko Wasada-Tsutsui, Hiroaki Wasada, and Hideki Masuda
  • Journal Title: Inorg. Chem. Volume: 52 Pages: 182-195
  • Peer Reviewed
• [Presentation] イオン液体中での電気化学的アンモニア合成 (2014)
  • Author(s): 片山精、猪股智彦、小澤智宏、増田秀樹
  • Organizer: 日本化学会&#39970;台４春季年会
  • Place of Presentation: 名古屋
• [Presentation] Syntheses and Reactivities of Dinuclear Copper Complexes as Structural/Functional Models of Tyrosinase (2013)
  • Author(s): H. Masuda
  • Organizer: The 2nd Japan-France Coordination Chemistry Symposium 2013
  • Place of Presentation: Nara, Japan
  • Invited
• [Presentation] Electrochemical Hydrogenation of Dinitrogen to Ammonia Using Titanocene Dichloride in an Ionic Liquid (2013)
  • Author(s): H. Masuda
  • Organizer: 4th Asian Conference on Coordination Chemistry (ACCC4)
  • Place of Presentation: Jeju, Korea
  • Invited
• [Presentation] 金属錯体の配位環境制御による機能発現 (2013)
  • Author(s): 増田秀樹
  • Organizer: 錯体化学会第63討論会
  • Place of Presentation: 琉球大学
  • Invited
• [Presentation] Electrochemical hydrogenation of dinitrogen to ammonia using titanocene dichloride in an ionic liquid (2013)
  • Author(s): Hideki Masuda
  • Organizer: 4th Asian Conference on Coordination Chemistry
  • Place of Presentation: Jeju Korea
  • Invited
• [Presentation] Electrochemical hydrogenation of dinitrogen to ammonia using titanocene dichloride in an ionic liquid and its evaluation of ionic liquid by SEIRAS (2013)
  • Author(s): Akira Katayama, Takahiko Ogawa, Tomohiko Inomata, Tomohiro Ozawa, and Hideki Masuda
  • Organizer: 錯体化学会第６３回討論会
  • Place of Presentation: 沖縄
• [Presentation] Electrochemical Hydrogenation of Dinitrogen to Ammonia Using Titanocene in ionic Liquids Containing FAP Anion, [(C2F5)3PF3]- (2013)
  • Author(s): A. Katayama, T. Suzuki, T. Ogawa, and H. Masuda
  • Organizer: 5th Interinational Symposium on Advanced Plasma Science and its Applications for Nitrides and Nanomaterials
  • Place of Presentation: Nagoya
• [Presentation] 金属酵素活性中心を規範とした金属錯体による酸素の活性化戦略 (2012)
  • Author(s): 増田秀樹
  • Organizer: 第45回酸化反応討論会
  • Place of Presentation: 名古屋市立大学
  • Invited
• [Presentation] 金属酵素を模倣した金属錯体による酸素の活性化 (2012)
  • Author(s): 増田秀樹
  • Organizer: 第22回金属の関与する生体関連反応シンポジウム
  • Place of Presentation: 金沢大学
  • Invited
• [Presentation] Electro-chemical Reduction of Dioxygen by Diiron(II) Complex in an Ionic Liquid Modified on Gold Electrode (2012)
  • Author(s): H. Masuda
  • Organizer: 9^<th> Japan-China Joint Symposium on Metal Cluster Compounds
  • Place of Presentation: Fukuoka, Japan
  • Invited
• [Presentation] Selective Preparation of (μ-η2 : η2-peroxo)dicopper(II) and Bis(μ-oxo) dicopper(III) Species as Hemocyanin and/or Tyrosinase Model (2012)
  • Author(s): H. Masuda
  • Organizer: 7^<th> Interational Conference on Porphyrins and Phthalocyanines (ICPP-7)
  • Place of Presentation: Jeju, Korea
• [Presentation] Study on synthesis and reactivity of iron complexes with SNS thioamide pincer-type ligand as nitrogenase mimic (2012)
  • Author(s): Tatsuya Suzuki and Hideki Masuda
  • Organizer: The 6th Asian Biological Inorganic Chemistry Conference
  • Place of Presentation: Hong Kong
• [Book] 化学版 これって英語で言えますか (2013)
  • Author(s): 斉藤勝弘、増田秀樹
  • Total Pages: 185
  • Publisher: 講談社サイエンティフィック
• [Book] 「物質・エネルギー変換の未来を拓く高機能材料の開発」超ハイブリッド材料ポリマーフロンティア21講演録シリーズ34 (2012)
  • Author(s): 増田秀樹
• [Book] 「健康・環境センサーの開発」ケミカルエンジニアリング、Vol. 57, No.1 (2012)
  • Author(s): 増田秀樹、小澤智宏、猪股智彦(共著)
  • Publisher: 化学工業社
• [Remarks]
  • URL: http://www.ach.nitech.ac.jp/~inorg/masuda/Japanese/
• [Patent(Industrial Property Rights)] 光増感剤 (2013)
  • Inventor(s): 増田秀樹，小澤智宏，舩橋靖博，猪股智彦，山本浩輔
  • Industrial Property Rights Holder: 名古屋工業大学
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2012-083440
  • Filing Date: 2013-04-02
• [Patent(Industrial Property Rights)] 光増感剤およびこれを用いた光起電力素子 (2013)
  • Inventor(s): 増田秀樹，小澤智宏，舩橋靖博，猪股智彦，川合佑弥
  • Industrial Property Rights Holder: 名古屋工業大学
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2012-131506
  • Filing Date: 2013-06-11
• [Patent(Industrial Property Rights)] アンモニア製造法およびアンモニア製造装置 (2012)
  • Inventor(s): 増田秀樹、松本純、小川崇彦、片山精、島崎龍司、佐藤彰倫
  • Industrial Property Rights Holder: 増田秀樹、松本純、小川崇彦、片山精、島崎龍司、佐藤彰倫
  • Industrial Property Rights Type: 特許
  • Filing Date: 2012-08-21