金属錯体の精密二次元集積による新規触媒機能の創出

• Project Area: Molecule Activation Directed toward Straightforward Synthesis
• Project/Area Number: 25105703
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Hokkaido University
• Principal Investigator: 原 賢二 北海道大学, 触媒化学研究センター, 准教授 (10333593)
• Project Period (FY): 2013-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000); Fiscal Year 2014: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000); Fiscal Year 2013: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
• Keywords: 触媒 / 金属錯体 / メソポーラス担体 / 細孔 / ルテニウム / アルカン / 酸化 / 選択性 / 単分子層 / 表面 / イソシアニド / ロジウム / ラマン / 水素化

Outline of Annual Research Achievements

従来の触媒化学は、触媒分子を設計・合成して溶液中で用いる均一系の触媒（分子触媒）と金属あるいは金属酸化物表面の特性を利用する不均一系触媒に大きく二分されてそれぞれが発展してきた。高効率・低環境負荷の物質変換プロセスの開発が希求される現在、触媒化学が果たすべき役割は大きい。触媒化学が社会に対して今後も継続的に貢献を行うためには、従来の学問分野の枠組みを超えた新しい触媒設計の概念が必要であろう。そこで本研究では、触媒調製の新しいアプローチとして、金属錯体を規整表面上に精密に集積することによって特異な触媒反応場を構築する手法を開発した。
今年度は、メソポーラス担体の細孔内部に選択的かつ精密に導入した触媒活性中心による特異な触媒機能の創出を目指した。ナノメートルサイズの規則的な細孔構造を有するメソポーラス材料の細孔空間を特殊な反応場ととらえて特異な触媒機能の発現を期待した。検討の結果、ビピリジンを骨格に有する規則性メソポーラス有機シリカの細孔表面上に固定化したルテニウム錯体が、アダマンタンなどのアルカンの3級C-H結合の選択的酸化反応に非常に高い選択性と触媒活性を有することを見出した。また、触媒の繰り返し利用性と安価な酸化剤であるNaClOを利用できる点も本系の特徴である。放射光施設でのXAFS測定により、活性な触媒種の同定を行うとともに、本触媒系を適用可能なアルカン基質の範囲を探索した。

Research Progress Status

26年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

26年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] High-Density Monolayers of Metal Complexes: Preparation and Catalysis (2014)
  • Author(s): Hara, K.; Sawamura, M.; Fukuoka, A.
  • Journal Title: The Chemical Record Volume: 14 Issue: 5 Pages: 869-878
  • DOI: 10.1002/tcr.201402031
  • Peer Reviewed
• [Journal Article] Entropically Favored Adsorption of Cellulosic Molecules onto Carbon Materials through Hydrophobic Functionalities (2014)
  • Author(s): Mizuho Yabushita、Hirokazu Kobayashi、Jun-ya Hasegawa、Kenji Hara、Atsushi Fukuoka
  • Journal Title: ChemSusChem Volume: Vol. 7 Issue: 5 Pages: 1443-1450
  • DOI: 10.1002/cssc.201301296
  • Peer Reviewed
• [Journal Article] Scalable and template-free production of mesoporous calcium carbonate and its potential to formaldehyde adsorbent (2014)
  • Author(s): S. Yamanaka, T. Oiso, Y. Kurahashi, H. Abe, K. Hara, T. Fujimoto, Y. Kuga
  • Journal Title: J. Nanoparticle Res Volume: Vol.16, No.2 Issue: 2 Pages: 2266-2266
  • DOI: 10.1007/s11051-014-2266-9
  • NAID: 120006345402
  • Peer Reviewed
• [Journal Article] Quantitative evaluation of ball-milling effect on hydrolysis of cellulose catalysed by activated carbons (2014)
  • Author(s): Mizuho Yabushita, Hirokazu Kobayashi, Kenji Hara, Atsushi Fukuoka
  • Journal Title: Catalysis Science & Technology Volume: 未定 Issue: 8 Pages: 2312-2317
  • DOI: 10.1039/c4cy00175c
  • NAID: 120005567725
  • Peer Reviewed
• [Journal Article] Selective hydrodeoxygenation of lignin-related 4-propylphenol into n-propylbenzene in water by Pt-Re/ZrO2 catalysts (2014)
  • Author(s): Hidetoshi Ohta, Bo Feng, Hirokazu Kobayashi, Kenji Hara, Atsushi Fukuoka
  • Journal Title: Catalysis Today Volume: 印刷中 Pages: 139-144
  • DOI: 10.1016/j.cattod.2014.01.022
  • NAID: 120005468152
  • Peer Reviewed
• [Journal Article] Effects of biomineralization peptide topology on the structure and catalytic activity of Pd nanomaterials (2014)
  • Author(s): Janairo J.I., Sakaguhi T., Hara K., Fukuoka A., Sakaguchi K.
  • Journal Title: Chemical Communication Volume: 50 Issue: 66 Pages: 9259-9262
  • DOI: 10.1039/c4cc04350b
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Preparation of Highly Dispersed Pt Nanoparticles Supported on Zeolite-templated Carbon and Catalytic Application in Hydrogenation Reaction (2014)
  • Author(s): Jiang, C.; Hara, K. Namba, K.; Kobayashi, H.; Ittisanronnachai, S.; Nishihara, H.; Kyotani, T.; Fukuoka, A.
  • Journal Title: Chemistry Letters Volume: 43 Issue: 11 Pages: 1794-1796
  • DOI: 10.1246/cl.140699
  • NAID: 130004677610
  • Peer Reviewed
• [Journal Article] Thin Film Structures of Metal-Organic Framework [Cu₃(BTC)₂(H₂O)₃]<i>_n</i> on TiO₂(110) (2014)
  • Author(s): Hashimoto, M.; Okajima, S.; Kondo, T.; Hara, K.; Chun, W.-J.
  • Journal Title: Electrochemistry Volume: 82 Issue: 5 Pages: 335-337
  • DOI: 10.5796/electrochemistry.82.335
  • NAID: 130004562463
  • ISSN: 1344-3542, 2186-2451
  • Peer Reviewed / Open Access
• [Journal Article] Study of the Catalyst for Hydrolysis of Cyclosiloxanes (2014)
  • Author(s): 吉井 泰雄, 菅野 周一, 松原 宏文, 川嵜 透, 原 賢二, 福岡 淳
  • Journal Title: KAGAKU KOGAKU RONBUNSHU Volume: 40 Issue: 5 Pages: 420-424
  • DOI: 10.1252/kakoronbunshu.40.420
  • NAID: 130004691067
  • ISSN: 0386-216X, 1349-9203
  • Peer Reviewed
• [Journal Article] High Density Monolayer of Diisocyanide on Gold Surface as a Platform of Supported Rh-catalyst for Selective 1,4-Hydrogenation of α,β-Unsaturated Carbonyl Compounds (2014)
  • Author(s): Jagtap, S.; Fukuoka, A.; Hara, K.
  • Journal Title: Chem. Commun. Volume: 50 Issue: 39 Pages: 5046-5048
  • DOI: 10.1039/c3cc48181f
  • NAID: 120005425352
  • Peer Reviewed
• [Journal Article] A Solid Chelating Ligand: Periodic Mesoporous Organosilica Containing 2,2-Bipyridine within the Pore Walls (2014)
  • Author(s): M. Waki, Y. Maegawa, K. Hara, Y. Goto, S. Shirai, Y. Yamada, N. Mizoshita, T. Tani, W.-J. Chun, S. Muratsugu, M. Tada, A. Fukuoka, and S. Inagaki
  • Journal Title: J. Am. Chem. Soc. Volume: 136 Issue: 10 Pages: 4003-4011
  • DOI: 10.1021/ja4131609
  • Peer Reviewed / Open Access
• [Journal Article] Probing Plasmonic Effects on the Raman Activity of Ag Nanoparticle-Based Nanostructures through Terphenyl Diisocyanide Adsorption (2014)
  • Author(s): Baraldi, G.; Lopez-Tobar, E.; Hara, K.; Sanchez-Cortes, S.; Gonzalo, J.
  • Journal Title: J. Phys. Chem. C Volume: 118 Issue: 9 Pages: 4680-4686
  • DOI: 10.1021/jp410628m
  • Peer Reviewed
• [Journal Article] Removal of Decamethylcyclopentasiloxane by Metal Oxide (2014)
  • Author(s): 菅野 周一, 川嵜 透, 松原 宏文, 原 賢二, 福岡 淳
  • Journal Title: KAGAKU KOGAKU RONBUNSHU Volume: 40 Issue: 2 Pages: 104-111
  • DOI: 10.1252/kakoronbunshu.40.104
  • NAID: 130003392463
  • ISSN: 0386-216X, 1349-9203
  • Peer Reviewed
• [Journal Article] 微量のエチレンを低温で除去する触媒 (2014)
  • Author(s): 原 賢二, 福岡 淳
  • Journal Title: KAGAKU TO SEIBUTSU Volume: 52 Issue: 4 Pages: 208-209
  • DOI: 10.1271/kagakutoseibutsu.52.208
  • NAID: 130005061437
  • ISSN: 0453-073X, 1883-6852
  • Peer Reviewed
• [Presentation] High Density Monolayer of Metal Complex on Structurally-Defined Surface: Preparation and Application in Catalysis (2015)
  • Author(s): Kenji Hara, Sachin Jagtap, Yoshinori Kaji and Atsushi Fukuoka
  • Organizer: The seventh biennial Australian Colloid and Interface Symposium (ACIS 2015)
  • Place of Presentation: ホバート(オーストラリア)
  • Year and Date: 2015-02-05
• [Presentation] メソポーラスシリカ担持白金ナノ粒子によるエチレンの低温除去 (2014)
  • Author(s): 原 賢二、江 川霞、横谷 卓郎、福岡 淳
  • Organizer: 第30 回ゼオライト研究発表会
  • Place of Presentation: タワーホール船堀（東京都江戸川区）
  • Year and Date: 2014-11-27
• [Presentation] High Density Monolayer of Metal Complex on Structurally Defined Surface (2014)
  • Author(s): Hara, K.
  • Organizer: Vietnam Malaysia International Chemical Congress (VIMCC)
  • Place of Presentation: ハノイ(ベトナム)
  • Year and Date: 2014-11-08
  • Invited
• [Presentation] High-density Monolayer of Metal Complex as a Novel Challenge in Heterogeneous Catalysis (2014)
  • Author(s): Kenji Hara, Sachin Jagtap, Yoshinori Kaji and Atsushi Fukuoka
  • Organizer: The 2nd International Conference on Organometallics and Catalysis (OM&Cat-2014)
  • Place of Presentation: 東大寺総合文化センター(奈良市)
  • Year and Date: 2014-10-27
• [Presentation] メソポーラスシリカ担持白金ナノ粒子によるエチレンの低温酸化除去 (2014)
  • Author(s): 原 賢二、江 川霞、横谷 卓郎、趙 曼倩、福岡 淳
  • Organizer: 第114回触媒討論会（依頼講演）
  • Place of Presentation: 広島大学東広島キャンパス（東広島市）
  • Year and Date: 2014-09-27
  • Invited
• [Presentation] メソポーラス有機シリカ担持ルテニウム錯体の触媒反応への応用 (2014)
  • Author(s): 石戸 信広、原 賢二、前川 佳史、稲垣 伸二、福岡 淳
  • Organizer: 第114回触媒討論会
  • Place of Presentation: 広島大学東広島キャンパス（東広島市）
  • Year and Date: 2014-09-27
• [Presentation] 規整表面上での高密度金属錯体固定化による触媒反応場の構築 (2014)
  • Author(s): 原 賢二
  • Organizer: 第114回触媒討論会（依頼講演）
  • Place of Presentation: 広島大学東広島キャンパス（東広島市）
  • Year and Date: 2014-09-26
  • Invited
• [Presentation] Self-Assembled Monolayer of MetalDiisocyanide Complexes on Gold Surface: Application in Selective Catalysis (2014)
  • Author(s): Kenji Hara, Sachin Jagtap, Yoshinori Kaji and Atsushi Fukuoka
  • Organizer: The 28th Conference of the European Colloid and Interface Society (ECIS 2014)
  • Place of Presentation: Limassol (キプロス)
  • Year and Date: 2014-09-12
• [Presentation] Self-Assembled Monolayer on Gold Surface for Metal Grafting and Catalytic Application (2014)
  • Author(s): Hara, K.
  • Organizer: IEEE International Nanoelectornics Conference (IEEE INEC 2014)
  • Place of Presentation: 北海道大学（札幌市）
  • Year and Date: 2014-07-28
  • Invited
• [Presentation] Densely Packed Monolayer of Metal Complexes on Gold Surface: Application in Selective Catalysis (2014)
  • Author(s): Kenji Hara, Sachin Jagtap, Yoshinori Kaji and Atsushi Fukuoka
  • Organizer: The XXVI International Conference on Organometallic Chemistry (ICOMC 2014)
  • Place of Presentation: ロイトン札幌 (札幌市)
  • Year and Date: 2014-07-17
• [Presentation] High-Density Monolayer of Metal Complex as a Novel Challenge in Heterogeneous Catalysis (2014)
  • Author(s): Hara, K.
  • Organizer: The 3rd Frontier Chemistry Center International Symposium
  • Place of Presentation: 北海道大学（札幌市）
  • Year and Date: 2014-06-14
  • Invited
• [Presentation] Low Temperature Oxidative Elimination of Ethylene over Pt Nanoparticles Supported on Mesoporous Silica (2014)
  • Author(s): Kenji Hara, Chuanxia Jiang, Atsushi Fukuoka
  • Organizer: The Seventh Tokyo Conference on Advanced Catalytic Science and Technology (TOCAT7)
  • Place of Presentation: 京都テルサ（京都市）
  • Year and Date: 2014-06-06
• [Presentation] Immobilization of Cu and Ru complexes to organic ligand in periodic mesoporous organosilicas (2014)
  • Author(s): Nobuhiro Ishito, Kenji Hara, Wang Jae Chun, Yoshifumi Maegawa, Shinji Inagaki, Atsushi Fukuoka
  • Organizer: The Seventh Tokyo Conference on Advanced Catalytic Science and Technology (TOCAT7)
  • Place of Presentation: 京都テルサ（京都市）
  • Year and Date: 2014-06-03
• [Presentation] Densely Packed Monolayer of Metal Complexes on Gold Surface: Application in Selective Catalysis (2014)
  • Author(s): Kenji Hara, Sachin Jagtap, Yoshinori Kaji and Atsushi Fukuoka
  • Organizer: TOCAT7 Pre-Symposium in Shiretoko“International Symposium on Catalysis for Renewable Chemicals”
  • Place of Presentation: 知床グランドホテル北こぶし(北海道斜里町)
  • Year and Date: 2014-05-30
• [Presentation] Immobilization of metal complexes on organic ligands in periodic mesoporous organosilicas (2014)
  • Author(s): Nobuhiro Ishito, Kenji Hara, Wang Jae Chun, Yoshifumi Maegawa, Shinji Inagaki, Atsushi Fukuoka
  • Organizer: TOCAT7 Pre-Symposium in Shiretoko“International Symposium on Catalysis for Renewable Chemicals”
  • Place of Presentation: 知床グランドホテル北こぶし(北海道斜里町)
  • Year and Date: 2014-05-30
• [Presentation] Surface Selective Silylation of Mesoporous Siica MCM-41; Precise Characterization and Cu Catalysis (2013)
  • Author(s): Kenji Hara, Saiko Akahane,Jerzy W. Wiench, Breina R. Burgin, Nobuhiro Ishito, Victor S.-Y. Lin, Marek Pruski and Atsushi Fukuoka
  • Organizer: 8th International Mesostructured Materials Symposium (IMMS2013)
  • Place of Presentation: 淡路夢舞台国際会議場(淡路市)
• [Presentation] Densely Packed Monolayer of Rh-Diisocynide on Gold Surface as Platforms for Highly Active and Selective Catalysis (2013)
  • Author(s): Hara, K. Jagtap, S.; Kaji, Y.; Namba, K.; Fukuoka, A.
  • Organizer: 17th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS17)
  • Place of Presentation: ﾘﾝｶｰﾝｾﾝﾀｰ （USA）
• [Presentation] ジイソシアニド単 分子層上に固定化したニッケルおよびコバト種を用いた水素化反応 (2013)
  • Author(s): 難波光太郎・原 賢二・福岡淳
  • Organizer: 第112回触媒討論会
  • Place of Presentation: 秋田大学（秋田市）
• [Presentation] メソポーラス有機シリカ上への銅およびルテニウム錯体の固定化 (2013)
  • Author(s): 石戸信広・原賢二・田旺帝・前川佳史・稲垣伸二・福岡淳
  • Organizer: 第112回触媒討論会
  • Place of Presentation: 秋田大学（秋田市）
• [Presentation] Immobilization of Cu complex to organic ligand in Periodic Mesoporous Organosilicas (2013)
  • Author(s): Nobuhiro Ishito,Kenji Hara, Yoshifumi Maegawa, Shinji Inagaki and Atsushi Fukuoka
  • Organizer: 8th International Mesostructured Materials Symposium (IMMS2013)
  • Place of Presentation: 淡路夢舞台国際会議場(淡路市)
• [Presentation] Direct C-H Borylation of Arenes Catalyzed by Iridium Complex Fixed on Bipyridine-bridged Periodic Mesoporous Organosilica (2013)
  • Author(s): 前川佳史、後藤康友、原賢二、福岡淳、石戸信広、田旺帝、稲垣伸二
  • Organizer: 第60回有機金属化学討論会
  • Place of Presentation: 学習院大学(東京都豊島区)
• [Presentation] メソポーラス有機シリカ上への銅錯体の固定化 (2013)
  • Author(s): 石戸信広、原賢二、前川佳史、稲垣伸二、福岡淳
  • Organizer: 第53回オーロラセミナー
  • Place of Presentation: ホテル花神楽（東神楽町）
• [Presentation] 規整表面上での金属錯体の高密度固定化による新規触媒の開発
  • Author(s): 原 賢二
  • Organizer: (3) 触媒学会千葉地区講演会「高付加価値生成物合成に向けた新規触媒の開発」
  • Place of Presentation: 千葉大学（千葉市）
  • Invited
• [Presentation] Densely Packed Monolayer of Metal-Diisocyanide on Gold Surface; Preparation and Application in Catalysis
  • Author(s): Kenji Hara
  • Organizer: Collaborative Conference on 3D & Materials Research 2013
  • Place of Presentation: Ramada Plaza Jeju Hotel（韓国）
  • Invited
• [Presentation] Densely Packed Monolayer of Metal Complex on Gold Surface: Application in Selective Catalysis
  • Author(s): Kenji Hara
  • Organizer: MANA Seminar
  • Place of Presentation: 物質・材料機構（つくば市）
  • Invited
• [Presentation] High density monolayer of Rh-diisocynide on gold surface as a platform for active and selective hydrogenation catalysis
  • Author(s): Hara, K. Jagtap, S.; Kaji, Y.; Fukuoka, A.
  • Organizer: The Sixteenth International Symposium on Relations between Homogeneous and Heterogeneous Catalysis (ISHHC-16)
  • Place of Presentation: 北海道大学（札幌市）
• [Presentation] 規整表面上での金属錯体の精密集積による新規触媒反応場の構築
  • Author(s): 原賢二
  • Organizer: 「分子活性化」第５回公開シンポジウム
  • Place of Presentation: イーグレ姫路あいめっせホール（姫路市）
• [Presentation] High-Density Monolayer of Metal Diisocyanide on Au Surface as a Promising Platform for Novel Catalysts
  • Author(s): Kenji Hara
  • Organizer: The 3rd International Symposium on Molecular Activation
  • Place of Presentation: Sheraton Steamboat Resort （USA）
• [Book] 触媒の設計・反応制御 事例集 (2013)
  • Author(s): 原 賢二
  • Publisher: 技術情報協会