研究者データベース

福岡 淳(フクオカ アツシ)
触媒科学研究所 物質変換研究部門
教授

基本情報

所属

  • 触媒科学研究所 物質変換研究部門

職名

  • 教授

学位

  • 工学博士(東京大学)

ホームページURL

科研費研究者番号

  • 80189927

J-Global ID

プロフィール

  • 固体触媒の分子設計とバイオマス変換

    私達の研究室は,北海道大学の附置研・センターである触媒化学研究センターの物質変換化学研究部門です.この部門は,平成19年の改組で生まれましたが,研究室の源流は触媒研究所(いわゆる触研)時代の酸塩基触媒部門であり,触媒化学研究センターでは触媒設計部門でした.それぞれ,田部浩三先生と市川勝先生という固体触媒の大御所の先生の研究室です.固体酸塩基触媒とシップインボトル合成・新エネルギー変換の研究は,固体触媒の新しい展開と応用を示し,時代を先取りした先駆的な業績でした.

    私も先輩たちに続き,このように時代を先取りするような仕事をしたいと思います.そのため,何が新規性・独創性をもつかを日々考えています.原賢二准教授と小林広和助教にはテーマ選定の相談相手になってもらい,さらに研究を実施してもらっています.理学部化学科の協力講座でもあるので,テーマとしては応用より基礎的な研究を行うことを重要視しています.ただ単に高い収率を求めて世界記録競争をすると,人海戦術でくる相手には太刀打ちできません.反応成績だけにこだわるのではなく,反応機構を論理的に考察することを重視しています.

    研究室の大きなテーマは,タイトルの左半分に書いたように「固体触媒の分子設計」です.これは,固体触媒の永遠のテーマと言っても過言ではありません.活性点と反応場を分子設計・合成することで,新規の反応を起こすことができれば素晴らしいことです.最近では,触媒反応場としてメソ多孔体の規則性細孔空間に興味をもっています.これは,触媒材料ありきで反応を探索する研究なので,ゼオライトやMOFではできないことをメソで行うことができるかがポイントになります.基礎を重視するとは言いながら,触媒反応としては,少しでも実用性のある反応を行うことを心がけています.燃料電池用水素の選択CO酸化(PROX)をきっかけとして,メソ多孔体が有効な担体になる反応を示していければと思います.

    もう一つの大きなテーマはバイオマス変換で,タイトルの右半分にあたります.従って,分子設計した触媒の応用の一つと捉えています.これは反応ありきで触媒材料を探索する研究ですが,きっかけは10年ほど前に遡ります.当時,私は独立の研究グループをもち,環境触媒関連の新しい反応を始めるためにいろいろと勉強していました.その際,奥原教授の総説(T. Okuhara, Chem. Rev., 102, 3641 (2002))にマルトースの加水分解反応が書かれているのを見つけ,糖の反応を行うことを思いつきました(このいきさつから,奥原先生は私のメンターの一人だと思っています).

    タイトルに書いた「固体触媒の分子設計と・・・」の「・・・」に入るものを考えるのは楽しいことです.課題解決型から好奇心追求型まで,いろいろな研究をあてはめることができるように思います.

研究キーワード

  • キチン   鮮度保持   エチレン酸化   ナノ粒子   メソポーラスシリカ   セルロース   バイオマス   触媒   Nanoparticle   Mesoporous Silica   Catalyst   Cellulose   Biomass   Catalyst   

研究分野

  • ナノテク・材料 / グリーンサステイナブルケミストリー、環境化学
  • ものづくり技術(機械・電気電子・化学工学) / 触媒プロセス、資源化学プロセス

職歴

  • 2015年10月 - 現在 北海道大学 触媒科学研究所 教授
  • 2014年04月 - 現在 北海道大学 総長補佐
  • 2007年04月 - 2015年09月 北海道大学 触媒化学研究センター 教授
  • 2010年04月 - 2014年03月 北海道大学 触媒化学研究センター センター長
  • 1997年04月 - 2007年03月 北海道大学 触媒化学研究センター 助教授
  • 1997年 - 2007年 Associate Professor,Catalysis Research Center, Hokkaido University
  • 2007年 Professor, Catalysis Research Center, Hokkaido University
  • 1995年08月 - 1997年03月 東京農工大学 工学部 助教授
  • 1995年 - 1997年 Associate Professor,Faculty of Technology, Tokyo University of Agriculture and Technology
  • 1991年04月 - 1995年07月 東京農工大学 工学部 講師
  • 1991年 - 1995年 Lecturer,Faculty of Technology, Tokyo University of Agriculture and Technology
  • 1989年05月 - 1991年03月 北海道大学 触媒化学研究センター 助手
  • 1989年 - 1991年 Research Associate,Catalysis Research Center, Hokkaido University
  • 1986年01月 - 1989年04月 北海道大学 触媒研究所 助手
  • 1986年 - 1989年 Research Associate,Research Institute for Catalysis, Hokkaido University

学歴

  • 1982年04月 - 1985年12月   東京大学   工学系研究科   工業化学専攻
  • 1978年04月 - 1982年03月   東京大学   工学部   合成化学科

所属学協会

  • アメリカ化学会   石油学会   ゼオライト学会   触媒学会   日本化学会   American Chemical Society   

研究活動情報

論文

  • Takuya Sagawa, Hirokazu Kobayashi, Chinatsu Murata, Yukatsu Shichibu, Katsuaki Konishi, Mineo Hashizume, Atsushi Fukuoka
    Bulletin of the Chemical Society of Japan 2022年05月27日
  • Jan J. Wiesfeld, Miyuki Asakawa, Takayuki Aoshima, Atsushi Fukuoka, Emiel J. M. Hensen, Kiyotaka Nakajima
    ChemCatChem 2022年04月21日
  • Tat Boonyakarn, Jan J Wiesfeld, Miyuki Asakawa, Lulu Chen, Atsushi Fukuoka, Emiel J M Hensen, Kiyotaka Nakajima
    ChemSusChem 15 7 e202200059  2022年04月07日 
    An acetal protection strategy for 5-hydroxymethylfurfural (HMF) was used to obtain 2,5-diformyfuran (DFF) using concentrated HMF solutions and a γ-Al2 O3 -supported Ru catalyst (Ru/γ-Al2 O3 ). The HMF-acetal with 1,3-propanediol can be oxidized to DFF-acetal with a yield of 84.0 % at an HMF conversion of 94.2 % from a 50 wt % solution. In contrast, aerobic oxidation of nonprotected HMF using a 10 wt % solution afforded DFF only in a moderate yield (52.3 %). Kinetic studies indicated that the six-membered ring acetal group not only prevents side reactions but also accelerates aerobic oxidation of the -CH2 OH moiety to -CHO under retention of the acetal functionality. Organic deposits formed during the reaction explained the significant decrease in the activity of the Ru/γ-Al2 O3 catalyst, which could be recovered neither by washing in water or organic solvents, nor by a calcination-reduction treatment. Sonication of the used Ru/γ-Al2 O3 catalyst in an aqueous NaOH solution successfully removed the deposits and allowed reuse of the catalyst for at least four times without activity loss.
  • Yayati Naresh Palai, Abhijit Shrotri, Atsushi Fukuoka
    ACS Catalysis 12 6 3534 - 3542 2022年03月18日
  • Takeshi Mori, Tatsuhiro Shigyo, Takafumi Nomura, Yuki Osanai, Kiyotaka Nakajima, Atsushi Fukuoka
    Catalysis Science & Technology 2022年 
    Silica-supported platinum catalysts can remove trace amounts of ethylene from perishables and extend their shelf-lives.
  • Nazmul Hasan MD Dostagir, Rattanawalee Rattanawan, Min Gao, Jin Ota, Jun-ya Hasegawa, Kiyotaka Asakura, Atsushi Fukuoka, Abhijit Shrotri
    ACS Catalysis 11 15 9450 - 9461 2021年08月06日 [査読有り]
  • Pengru Chen, Abhijit Shrotri, Atsushi Fukuoka
    Applied Catalysis A: General 621 118177 - 118177 2021年07月 [査読有り]
  • Ryota Osuga, Shuhei Yasuda, Masato Sawada, Ryo Manabe, Hisashi Shima, Susumu Tsutsuminai, Atsushi Fukuoka, Hirokazu Kobayashi, Atsushi Muramatsu, Toshiyuki Yokoi
    Industrial & Engineering Chemistry Research 60 24 8696 - 8704 2021年06月23日 [査読有り]
     
    Rh ion-exchanged Y zeolite (Rh-Y) and amorphous silica-alumina (Rh-ASA) were prepared by the ion-exchange method. The Rh species were identified by UV-vis and IR spectroscopies, TEM, and H2-TPR measurements. Isolated Rh cations were preferentially formed on the Y zeolite, while Rh oxide mainly existed on ASA. The catalytic activities of the prepared samples for oxidative reforming of methane were evaluated. The Rh oxide on Rh-ASA exhibited slightly higher methane conversion and CO yield than those of the isolated Rh cation on Rh-Y. On the other hand, the catalytic lifetime over Rh-Y was longer than that over Rh-ASA because the isolated Rh cations were protected from aggregation by electrostatic interaction with the zeolite framework. In addition, Rh-Y exhibited a high catalytic activity even at low Rh contents owing to its high dispersibility. On the basis of the experimental facts, we have successfully clarified the active Rh species for this oxidative reforming of methane and demonstrated the effectiveness of the zeolite framework for the stabilization of the active species. This article provides the important concept for the design of highly active catalysts in this catalytic system.
  • Lingcong Li, Nazmul H. MD Dostagir, Abhijit Shrotri, Atsushi Fukuoka, Hirokazu Kobayashi
    ACS Catalysis 11 7 3782 - 3789 2021年04月02日 [査読有り]
  • Yayati Naresh Palai, Abhijit Shrotri, Miyuki Asakawa, Atsushi Fukuoka
    Catalysis Today 365 241 - 248 2021年04月 [査読有り]
  • Danjo De Chavez, Hirokazu Kobayashi, Atsushi Fukuoka, Jun-ya Hasegawa
    The Journal of Physical Chemistry A 125 1 187 - 197 2021年01月14日 [査読有り]
  • Yue Rong, Na Ji, Zhihao Yu, Xinyong Diao, Hanyang Li, Yaxuan Lei, Xuebin Lu, Atsushi Fukuoka
    Green Chemistry 23 18 6761 - 6788 2021年 
    Using lignin derivatives as substrates, important organic nitrogen chemicals such as aniline and benzylamine can be obtained with high selectivity through heterogeneous catalyzed amination.
  • Cheng Yang, Takuya Sagawa, Atsushi Fukuoka, Hirokazu Kobayashi
    Green Chemistry 23 18 7228 - 7234 2021年 [査読有り]
     
    H3PO3 converts a chitin-derived sugar alcohol to a potential monomer for polymer production by a mechanism different from that for strong acid catalysts.
  • Hirokazu Kobayashi, Yusuke Suzuki, Takuya Sagawa, Kyoichi Kuroki, Jun-ya Hasegawa, Atsushi Fukuoka
    Physical Chemistry Chemical Physics 23 30 15908 - 15916 2021年 [査読有り]
     

    Compressive forces produced by ball-milling can activate glycosidic bonds of polysaccharides towards mechanocatalytic hydrolysis.

  • Takuya Sagawa, Hirokazu Kobayashi, Atsushi Fukuoka
    Molecular Catalysis 498 111282  2020年12月 [査読有り][通常論文]
  • Shuhei Yasuda, Ryota Osuga, Yusuke Kunitake, Kazuya Kato, Atsushi Fukuoka, Hirokazu Kobayashi, Min Gao, Jun-ya Hasegawa, Ryo Manabe, Hisashi Shima, Susumu Tsutsuminai, Toshiyuki Yokoi
    Communications Chemistry 3 1 2020年12月 [査読有り]
     
    AbstractThe development of simple catalysts with high performance in the selective oxidation of methane to syngas at low temperature has attracted much attention. Here we report a nickel-based solid catalyst for the oxidation of methane, synthesised by a facile impregnation method. Highly dispersed ultra-small NiO particles of 1.6 nm in size are successfully formed on the MOR-type zeolite. The zeolite–supported nickel catalyst gives continuously 97–98% methane conversion, 91–92% of CO yield with a H2/CO ratio of 2.0, and high durability without serious carbon deposition onto the catalyst at 973 K. DFT calculations demonstrate the effect of NiO particle size on the C-H dissociation process of CH4. A decrease in the NiO particle size enhances the production of oxygen originating from the NiO nanoparticles, which contributes to the oxidation of methane under a reductive environment, effectively producing syngas.
  • Shazia S. Satter, Jun Hirayama, Hirokazu Kobayashi, Kiyotaka Nakajima, Atsushi Fukuoka
    ACS Catalysis 10 22 13257 - 13268 2020年11月20日 [査読有り]
     
    The structure-activity relationship of silica-supported Pt catalysts in aerobic oxidation of 50 ppm ethylene was studied at 0 degrees C with a fixed-bed flow reactor and in situ characterization techniques using Fourier-transform infrared (FTIR) spectroscopy. The activity of all Pt catalysts examined here decreased by water molecules formed during stoichiometric oxidation of ethylene and became stable steadily. A mesoporous silica-supported Pt catalyst improved its steady-state activity after calcination of the support in air at 800 degrees C, whereas no such effect was observed for a nonporous silica support. CO-pulse titration, H2O adsorption measurements, Si-29 MAS NMR, and in situ FTIR along with catalytic activity studies revealed that the activity of the mesoporous silica-supported Pt catalyst is higher than that of nonporous silica-supported ones, despite showing similar hydrophobicity and low Pt dispersion. In situ characterization using CO as a molecular probe indicates that a part of the Pt surface inside hydrophobic mesopores is not involved in the hydrogenbonding network among physisorbed water molecules and surface SiOH groups even after full hydration of the catalyst surface, and bare Pt sites are expected to work more effectively for ethylene oxidation. Such a "hydrophobic Pt surface" can only be formed on a hydrophobic mesoporous silica support, which is probably because of Pt nanoparticles surrounded by a hydrophobic siloxane network entirely. A unique environment derived from the condensed siloxane network and restricted mesopores contributes largely to the high activity of Pt nanoparticles for low-temperature oxidation of trace ethylene.
  • Lina Mahardiani, Abhijit Shrotri, Hirokazu Kobayashi, Atsushi Fukuoka
    Catalysis Today 357 409 - 415 2020年11月 [査読有り]
  • Daniele Padovan, Hirokazu Kobayashi, Atsushi Fukuoka
    ChemSusChem 13 14 3594 - 3598 2020年07月22日 [査読有り]
  • Mizuho YABUSHITA, Atsushi FUKUOKA
    Journal of the Japan Petroleum Institute 63 4 163 - 171 2020年07月01日 [査読有り]
  • Jun Hirayama, Hirokazu Kobayashi, Atsushi Fukuoka
    Bulletin of the Chemical Society of Japan 93 2 273 - 278 2020年02月15日 [査読有り]
  • Minjune Kim, Silvia Ronchetti, Barbara Onida, Nobuyuki Ichikuni, Atsushi Fukuoka, Hideki Kato, Kiyotaka Nakajima
    ChemCatChem 12 1 350 - 359 2020年01月08日 [査読有り]
     
    Amphoteric YNbO4 was synthesized by the simple coprecipitation using (NH4)(3)[Nb(O-2)(4)] and Y(NO3)(3), and examined as a new solid acid-base bifunctional catalyst for various reactions including aqueous-phase conversion of glucose to lactic acid. After drying the white precipitate at 353 K for 3 h, the resultant oxide is an amorphous YNbO4 with high densities of Lewis acid sites (0.18 mmol g(-1)) and base sites (0.38 mmol g(-1)). Negatively-charged lattice oxygen of amorphous YNbO4 functioned as Lewis base sites that promote a Claisen-Schmidt-type condensation reaction with acetylacetone and benzaldehyde with comparable activity to reference catalysts. Amorphous YNbO4 can also be applicable to the production of lactic acid from glucose in water, which gives relatively high yields (19.6 %) compared with other reference catalysts. Mechanistic studies using glucose-1-d and H-2 nuclear magnetic resonance spectroscopy (NMR) revealed that YNbO4 first converts glucose to two carbohydrates (glyceraldehyde and pyruvaldehyde) through dehydration via the formation of 3-deoxyglucosone and subsequent retro-aldolization, and these intermediates are then converted to lactic acid by both dehydration and isomerization through hydride transfer.
  • Pengru Chen, Abhijit Shrotri, Atsushi Fukuoka
    Catalysis Science & Technology 10 14 4593 - 4601 2020年 

    Larger cello-oligosaccharides undergo faster hydrolysis over carbon catalysts. This is attributed to reduction in activation energy caused by conformational change in the structure of oligosaccharides as they adsorb within the micropores of carbon.

  • Nazmul Hasan MD Dostagir, Coogan Thompson, Hirokazu Kobayashi, Ayman M. Karim, Atsushi Fukuoka, Abhijit Shrotri
    Catalysis Science & Technology 10 24 8196 - 8202 2020年 [査読有り]
     

    Atomically dispersed Rh promoted the activity of In2O3 for methanol formation from CO2, inducing strong CO2 adsorption and enhanced formate formation.

  • Ryota Osuga, Saikhantsetseg Bayarsaikhan, Shuhei Yasuda, Ryo Manabe, Hisashi Shima, Susumu Tsutsuminai, Atsushi Fukuoka, Hirokazu Kobayashi, Toshiyuki Yokoi
    Chemical Communications accepted 44 5913 - 5916 2020年 [査読有り][通常論文]
     
    Rh ion-exchanged MFI-type aluminosilicate zeolites with different Al distributions were prepared for controlling the location, state, and size of Rh species. The MFI-type aluminosilicate zeolite with the framework Al atoms predominantly located inside the channel intersections leads to the formation of relatively large Rh species, which were confirmed by ultraviolet-visible (UV-vis) and infrared (IR) spectroscopies. Moreover, this catalyst showed a high catalytic activity for the oxidative reforming reaction of methane.
  • Mizuho Yabushita, Gabriella Papa, Peng Li, Atsushi Fukuoka, Omar K. Farha, Blake A. Simmons, Alexander Katz
    Fuel Processing Technology 197 106189 - 106189 2020年01月 [査読有り]
  • Yuichi Nishimura, Manato Suda, Mai Kuroha, Hirokazu Kobayashi, Kiyotaka Nakajima, Atsushi Fukuoka
    Carbohydrate Research 486 107826 - 107826 2019年12月 [査読有り]
     
    An efficient and environmentally friendly system for producing 5-hydroxymethylfurfural (5-HMF) from fructose has been proposed. Substrate concentration is an important factor for practical application of the process; however, use of a high concentration of fructose has rarely been tested in the reaction because the conditions accelerate intermolecular side reactions to form adhesive humins. Humin by products stuck on reactor surfaces can make the production of 5-HMF on an industrial scale difficult. Therefore, developing a catalytic reaction system that can promote the synthesis of 5-HMF from highly concentrated fructose without causing adhesion of humins to reactors is needed. The present study demonstrated that activated carbons are promising materials for this system. Activated carbon catalyzed the conversion of fructose to 5-HMF without adhesion of humins to reactor vessels under practical conditions of high substrate concentration up to 73.2%. The catalytic activity was determined not only by the amount of surface weakly acidic oxygenated groups but also by the adsorption of fructose. In addition, strong adsorption of 5-HMF led to low selectivity of 5-HMF and the formation of adhesive humins. This is the first report to describe the synthesis of 5-HMF from solutions containing a fructose concentration greater than 70%.
  • Cheng Yang, Hirokazu Kobayashi, Atsushi Fukuoka
    Fuel Processing Technology 196 106155 - 106155 2019年12月 [査読有り]
  • Hidetoshi Ohta, Kanako Tobayashi, Akihiro Kuroo, Mao Nakatsuka, Hirokazu Kobayashi, Atsushi Fukuoka, Go Hamasaka, Yasuhiro Uozumi, Haruno Murayama, Makoto Tokunaga, Minoru Hayashi
    Chemistry – A European Journal 25 65 14762 - 14766 2019年11月22日 [査読有り]
     
    The selective and efficient removal of oxygenated groups from lignin-derived phenols is a critical challenge to utilize lignin as a source for renewable aromatic chemicals. This report describes how surface modification of a zeolite-supported Pt catalyst using ionic liquids (ILs) remarkably increases selectivity for the hydrodeoxygenation (HDO) of phenols into arenes under mild reaction conditions using atmospheric pressure H2. Unmodified Pt/H-ZSM-5 converts phenols into aliphatic species as the major products along with a slight amount of arenes (10 % selectivity). In contrast, the catalyst modified with an IL, 1-butyl-3-methylimidazolium triflate, keeps up to 76 % selectivity for arenes even at a nearly complete conversion of phenols. The IL on the surface of Pt catalyst may offer the adsorption of phenols in an edge-to-face manner onto the surface, thus accelerating the HDO without the ring hydrogenation.
  • Hirokazu Kobayashi, Atsushi Fukuoka
    炭素 2019 290 211 - 218 2019年11月15日 [査読有り][招待有り]
  • Danjo P. De Chavez, Min Gao, Hirokazu Kobayashi, Atsushi Fukuoka, Jun-ya Hasegawa
    Molecular Catalysis 475 110459 - 110459 2019年10月 [査読有り]
     
    Carboxylic acid and phenol moiety containing carbon materials are proven to catalyze cellulose hydrolysis. Experiments utilizing benzoic acid and substituted derivatives as model catalysts revealed that vicinal oxygenated group containing catalysts showed significantly higher activities regardless of acidity. However, the increase in catalytic activity was not well understood. Using density functional theory, the mechanism of catalysis was elucidated. Calculated binding energy followed the experimental turnover number suggesting that the formation and the stability of the adduct complex is imperative to catalysis. In addition to this, protonated system effectively modeled the experimental activation energy implying that a hydronium participates in the reaction. These calculations indicated that during the life time of the adduct complex, a dissolved proton assists in the overall catalytic mechanism.
  • Takuya Sagawa, Hirokazu Kobayashi, Chinatsu Murata, Yukatsu Shichibu, Katsuaki Konishi, Atsushi Fukuoka
    ACS Sustainable Chemistry & Engineering 7 17 14883 - 14888 2019年09月03日 [査読有り]
  • Pengru Chen, Abhijit Shrotri, Atsushi Fukuoka
    ChemSusChem 12 12 2576 - 2580 2019年06月21日 [査読有り]
  • Ray Miyazaki, Naoki Nakatani, Sergey V. Levchenko, Takuro Yokoya, Kiyotaka Nakajima, Kenji Hara, Atsushi Fukuoka, Jun-ya Hasegawa
    The Journal of Physical Chemistry C 123 20 12706 - 12715 2019年05月23日 [査読有り]
     
    Low-temperature complete oxidation of ethylene by the mesoporous silica-supported Pt catalyst is a forefront technology for food preservation. Public implementations of the Pt catalyst have already begun, and spectroscopy analyses on the catalytic mechanism have been reported. In this study, density functional theory calculations were conducted to clarify the potential energy profile and electronic mechanism of the catalytic reaction. Based on the experimental findings, a reaction pathway was proposed for ethylene oxidation up to CO2 formation via the HCHO intermediate. Among several possibilities, a reaction pathway via ethylene dioxide species is energetically plausible for the C-C bond cleavage to generate HCHO. Particular focus was given to the electronic effect of the silica support in the ethylene dioxide route. The reservoir effect, in which the siloxide groups take electrons from the Pt moiety, reduces the activation energy of the C-C bond cleavage step by taking electrons from sigma(C-C) orbital.
  • Minjune Kim, Yaqiong Su, Takayuki Aoshima, Atsushi Fukuoka, Emiel J. M. Hensen, Kiyotaka Nakajima
    ACS Catalysis 9 5 4277 - 4285 2019年05月03日 [査読有り]
     
    A unique strategy for the formation of furan-2,5-dicarboxylic acid (FDCA)-derived esters with methanol and ethylene glycol in concentrated solutions was reported using a six-membered ring acetal of (5-hydroxymethypfurfural (HMF) with 1,3-propanediol in order to improve the economics for the production of polyethylene 2,5-furandicarboxylate (PEF), a biobased polyester. Aerobic oxidative esterification with methanol and ethylene glycol in the presence of a CeO2 -supported Au catalyst gave 80-95% yields of methyl furan-2,5-dicarboxylate and bis(2-hydroxyethyl)furan-2,5-dicarboxylate from concentrated HMF-acetal solutions (10-20 wt %). Kinetic studies combined with density functional theory (DFT) calculations were used to identify two key steps for the conversion of the cyclic acetal ring to the corresponding methyl ester: (i) partial hydrolysis of the acetal ring by OH- ions and (ii) subsequent oxidation of the hemiacetal in solution by molecular O-2 on Au nanoparticles. These results represent a significant contribution not only to cutting-edge conversion technology for renewable biomass feedstocks to PEF-based applications but also to opportunities for the efficient conversion of substrates with a reactive formyl group in high yield.
  • Abu Bin Ihsan, Yasuhiro Tawara, Shinya Goto, Hirokazu Kobayashi, Kiyotaka Nakajima, Atsushi Fukuoka, Yasuhito Koyama
    Polymer Journal 51 4 413 - 422 2019年04月 [査読有り]
     
    We developed 2,5-furanylene sulfide-containing polymers bearing different spacers as repeating units and evaluated the interactions between the furanylene sulfide units in the polymers. The treatment of 2,5-dichlorofuran derivatives with dithiolates at 200 degrees C promotes polycondensation via nucleophilic aromatic substitution to give the corresponding furanylene sulfide-containing polymers. Tensile measurements and spectral analyses demonstrate that the furanylene sulfide moieties form remarkably stable pi-pi stacking structures based on the enhanced dipole moment induced by sulfur linkages When the polymer has a long spacer between repeating furanylene sulfide units, the polymer behaves as a chemically stable network polymer comprised of pi-pi stacking structures as cross-linking units.
  • Mizuho Yabushita, Natsumi Shibayama, Kiyotaka Nakajima, Atsushi Fukuoka
    ACS Catalysis 9 3 2101 - 2109 2019年03月01日 [査読有り]
     
    A combination of ethanol solvent and hydrotalcite (HT) with a Mg/Al ratio of 3:1 was effective for the isomerization of glucose to fructose in up to 56% yield with a high selectivity of 80%. The ethanol solvent shifts the isomerization equilibrium between glucose and fructose, which allows the fructose yield to exceed the upper limit of enzymatic isomerization conducted in water at modest temperatures (i.e., 50%). The HT catalyst maintained such high catalytic performance in repeated use at least three times via calcination and subsequent reconstruction of the original layered structure by the memory effect, which was operated in an aqueous solution containing ammonium carbonate. The results of catalyst screening, characterization, and isotope tracer analysis have revealed that the base sites of HT mainly contribute to its high catalytic activity for glucose-to-fructose isomerization.
  • 触媒法バイオマス変換による基幹化学品合成
    佐川 拓矢, 中島 清 隆, 福岡 淳
    触媒 61 4 182 - 188 2019年 [査読無し][招待有り]
  • ゼオライト担持金属触媒を用いたメタンの部分酸化によるCO、H2合成
    小林広和, 福岡淳
    クリーンエネルギー 28 1 39 - 44 2019年01月 [査読無し][招待有り]
  • Miyuki Asakawa, Abhijit Shrotri, Hirokazu Kobayashi, Atsushi Fukuoka
    Green Chemistry 21 22 6146 - 6153 2019年 [査読有り]
     

    Furfural was synthesized from hexose sugars instead of 5-HMF by using polar aprotic solvents with very low basicity.

  • Yuhui Hou, Shinichi Nagamatsu, Kiyotaka Asakura, Atsushi Fukuoka, Hirokazu Kobayashi
    Communications Chemistry 1 1 2018年12月 [査読有り]
  • Mizuho Yabushita, Nicolás A. Grosso-Giordano, Atsushi Fukuoka, Alexander Katz
    ACS Applied Materials & Interfaces 10 46 39670 - 39678 2018年11月21日 [査読有り]
  • Kota Techikawara, Hirokazu Kobayashi, Atsushi Fukuoka
    ACS Sustainable Chemistry & Engineering 6 9 12411 - 12418 2018年09月04日 [査読有り]
  • Shazia S. Satter, Takuro Yokoya, Jun Hirayama, Kiyotaka Nakajima, Atsushi Fukuoka
    ACS Sustainable Chemistry & Engineering 6 9 11480 - 11486 2018年09月04日 [査読有り]
     
    Oxidation of trace ethylene (50 ppm) at 0 degrees C was systematically studied using Pt nanoparticles supported on mesoporous silica (SBA-15) in a fixed-bed flow reactor. The SBA-15 supported Pt catalyst (1.8 wt % Pt loading) exhibited an ethylene conversion higher than 99% at the initial stage, which gradually began to decrease at 90 min and reached 33% within 240 min. The CO2 yield was lower than the corresponding ethylene conversion before the steady state was reached. This was due to the formation of intermediates that were stabilized on the catalyst surface. These intermediates could be recovered in the form of CO2 by heating the spent catalyst in a mixed N-2 and He (1:19, v/v) flow at 150 degrees C. The addition of water vapor to the catalyst bed decreased the original activity drastically because physically adsorbed water molecules partly blocked the active Pt sites. Control experiments using nonordered silica supports (Aerosil 380 and 200) showed similar catalytic behavior as that observed with SBA-15. The formation of highly dispersed Pt nanoparticles on the silica surfaces is thus the key to the development of effective Pt catalysts for low-temperature oxidation of ethylene.
  • Shazia S. Satter, Jun Hirayama, Kiyotaka Nakajima, Atsushi Fukuoka
    Chemistry Letters 47 8 1000 - 1002 2018年08月05日 [査読有り]
     
    Hydrophobic SBA-15 has been found to improve catalytic activity of supported Pt nanoparticles for ethylene oxidation at 0 degrees C. Pt nanoparticles stabilized inside the hydrophobic mesopores enabled smooth ethylene conversion and CO2 formation at a steady state due to constant removal of physisorbed water formed during ethylene oxidation.
  • Minjune Kim, Yaqiong Su, Atsushi Fukuoka, Emiel J. M. Hensen, Kiyotaka Nakajima
    Angewandte Chemie International Edition 57 27 8235 - 8239 2018年07月02日 [査読有り]
     
    The utilization of 5-(hydroxymethyl)furfural (HMF) for the large-scale production of essential chemicals has been largely limited by the formation of solid humin as a byproduct, which prevents the operation of stepwise batch-type and continuous flow-type processes. The reaction of HMF with 1,3-propanediol produces an HMF acetal derivative that exhibits excellent thermal stability. Aerobic oxidation of the HMF acetal with a CeO2-supported Au catalyst and Na2CO3 in water gives a 90-95% yield of furan 2,5-dicarboxylic acid, an increasingly important commodity chemical for the biorenewables industry, from concentrated solutions (10-20 wt%) without humin formation. The six-membered acetal ring suppresses thermal decomposition and self-polymerization of HMF in concentrated solutions. Kinetic studies supported by DFT calculations identify two crucial steps in the reaction mechanism, that is, the partial hydrolysis of the acetal into 5-formyl-2-furan carboxylic acid involving OH- and Lewis acid sites on CeO2, and subsequent oxidative dehydrogenation of the in situ generated hemiacetal involving Au nanoparticles. These results represent a significant advance over the current state of the art, overcoming an inherent limitation of the oxidation of HMF to an important monomer for biopolymer production.
  • Sho Yamaguchi, Mizuho Yabushita, Minjune Kim, Jun Hirayama, Ken Motokura, Atsushi Fukuoka, Kiyotaka Nakajima
    ACS Sustainable Chemistry & Engineering 6 7 8113 - 8117 2018年07月02日 [査読有り]
     
    We report the catalytic conversion of biomass-derived carbohydrates to methyl lactate using metal oxides. The combination of Lewis acid-base sites on gamma-Al2O3 is superior to several amphoteric oxides for the production of methyl lactate from both dihydroxyacetone and glucose in methanol. The successful production of methyl lactate from glucose by gamma-Al2O3 is attributed to high densities of both acid and base functionalities that are essential for the promotion of the stepwise reaction, which consists of isomerization, retro-aldol, and dehydration reactions.
  • Abhijit Shrotri, Hirokazu Kobayashi, Atsushi Fukuoka
    Accounts of Chemical Research 51 3 761 - 768 2018年03月20日 [査読有り]
  • Navneet Kumar Gupta, Atsushi Fukuoka, Kiyotaka Nakajima
    ACS Sustainable Chemistry & Engineering 6 3 3434 - 3442 2018年03月05日 [査読有り]
     
    Aerobic oxidation of biomass-derived furfural to furoic acid was studied with an N-heterocyclic carbene as a homogeneous catalyst. Carbene species generated in situ on 1,3-bis(2,4,6-trimethylphenyl) imidazolium chloride with a strong organic base (1,8-diazabicyclo[5.4.0]undec-7-ene) was highly active and selective for the formation of furoic acid in dimethyl sulfoxide at 40 degrees C. This reaction initiates the formation of a Breslow intermediate between an N-heterocyclic carbene and a furfural molecule and the subsequent activation of molecular O-2. While the active carbene catalyst promoted furfural dimerization to afford furoin as a side reaction, furoin was decomposed into the Breslow intermediate and furfural through a reverse reaction, which were then converted quantitatively to furoic acid. Kinetic studies revealed that the apparent activation energy for this furfural oxidation was only 20 kJ mol(-1), which is significantly lower than that with a supported Au catalyst (30.4 kJ mol(-1)). The N-heterocyclic carbene catalyst can oxidize various furan-based aldehydes with high selectivity; however, the electron withdrawing group bonded to the furan ring has a negative effect on the reaction rate. Furfural can also be oxidized selectively to furoic acid, even in the presence of byproducts that are formed by acid-catalyzed dehydration of xylose with Amberlyst-70. As a result, a sequential reaction system based on initial dehydration and subsequent aerobic oxidation was developed for the production of furoic acid from xylose, without the need for furfural purification, using Amberlyst-70 (a solid acid) and an N-heterocyclic carbene catalyst.
  • Shino Sato, Shigeru Iwase, Kotaro Namba, Tomoya Ono, Kenji Hara, Atsushi Fukuoka, Kohei Uosaki, Katsuyoshi Ikeda
    ACS Nano 12 2 1228 - 1235 2018年02月27日 [査読有り]
  • Hirokazu Kobayashi, Atsushi Fukuoka
    Bulletin of the Chemical Society of Japan 91 1 29 - 43 2018年 [査読有り][通常論文]
     
    The efficient catalytic conversion of lignocellulose is a formidable issue, but it is worth studying in terms of the high potential as renewable chemical feedstock. In this account, we describe our approach to convert solid cellulose with solid catalysts. We found that carbons bearing weak acid sites were active for the hydrolysis of cellulose. The catalyst produced glucose in up to 88% yield after the formation of good solidsolid contact, due to selective enhancement of the solidsolid interfacial reaction. We also developed a cyclic system to efficiently convert real lignocellulosic biomass. Mechanistic study has revealed that polycyclic carbon aromatics attract cellulose by CHp interactions mainly consisting of dispersion forces and hydrophobic interactions. The adsorbed cellulose molecules diffuse on the surface, rapidly penetrate even micropores, and undergo hydrolysis by weak acid sites such as carboxylic acids. Phenolic or carboxylic groups adjacent to the weak acid increase the frequency factor by forming hydrogen bonds. The combined functions of carbon derived from both polar and nonpolar groups achieve the hydrolysis of cellulose. Finally, we comment on future perspective to apply these findings.
  • Nakajima, K., Hirata, J., Kim, M., Gupta, N.K., Murayama, T., Yoshida, A., Hiyoshi, N., Fukuoka, A., Ueda, W.
    ACS Catalysis 8 1 283 - 290 2018年 [査読有り][通常論文]
  • Nobuhiro Ishito, Kiyotaka Nakajima, Yoshifumi Maegawa, Shinji Inagaki, Atsushi Fukuoka
    CATALYSIS TODAY 298 258 - 262 2017年12月 [査読有り][通常論文]
     
    Outline Highlights Abstract Graphical abstract Keywords 1. Introduction 2. Experimental 3. Results and discussion 4. Conclusions References Show full outline Figures (9) Unlabelled figure Scheme 1. Formation of Au complex on BPy-PMO Fig. 1. (a) Au L3-edge XANES, (b) EXAFS oscillation, (c) Fourier transforms of EXAFS Fig. 2. (a) N2 adsorption isotherms and (b) NLDFT pore diameter distribution curves of Fig. 3. XRD patterns of BPy-PMO (black line) and AuNPs/BPy-PMO (blue line) in (a) low Fig. 4. (a) N2 adsorption isotherms and (b) XRD patterns of bare (black line) and Show all figures Elsevier Catalysis Today Volume 298, 1 December 2017, Pages 258-262 Catalysis Today Facile formation of gold nanoparticles on periodic mesoporous bipyridine-silica Silica-supported gold nanoparticles (AuNPs) can be synthesized on a bipyridine incorporated periodic mesoporous organosilica (BPy-PMO) as an inorganic support. Reaction of a bipyridine group in the periodic mesoporous organosilica with HAuCl4 forms an AuCl2-based complex, and its structure corresponds to a homogeneous complex, [AuCl2(bpy)]Cl. Thermal reduction of the complex in H-2 results in the formation of small gold nanoparticles with an average size of ca. 3.8 nm. Combined with nitrogen adsorption, XRD, UV/Vis, TEM, and XAFS measurements, it is demonstrated that uniform gold nanoparticles are homogeneously distributed inside mesopores. The size and distribution of gold nanoparticles are mainly controlled by strong interaction of surface metallic Au with pore walls of the periodic mesoporous organosilica. AuNPs/BPy-PMO shows higher catalytic activity than Au/MCM-41 in aerobic oxidation of benzaldehyde. (C) 2017 Elsevier B.V. All rights reserved.
  • Yuhui Hou, Sho Ogasawara, Atsushi Fukuoka, Hirokazu Kobayashi
    CATALYSIS SCIENCE & TECHNOLOGY 7 4 6132 - 6139 2017年12月 [査読有り][通常論文]
     
    The conversion of methane to syngas under mild conditions is a key to efficiently utilise natural gas, including shale gas, in chemical industries. In this work, we demonstrate that Rh sub-nano clusters formed on zeolites catalyse the partial oxidation of methane to syngas at substantially lower temperatures (450-600 degrees C) than those required in previous reports (>700 degrees C). Rh sub-nano clusters of 0.6 nm diameter were prepared by a simple ion-exchange method. The catalyst gave 84% conversion of methane with 91% selectivity for CO and a H-2/CO ratio of 2.0 at 600 degrees C even at a very high space velocity (1200000 mL h(-1) g(-1)). No deactivation was observed in the durability test for 50 h, and the turnover number of bulk Rh for the formation of CO reached 2600000. Kinetic and spectroscopic studies revealed that a combustion-reforming mechanism occurs on the metallic Rh sub-nano clusters. The acidity of the zeolite played no role in the reaction, but the ion-exchange properties of zeolites were crucial to prepare the active Rh catalysts.
  • Abhijit Shrotri, Hirokazu Kobayashi, Hiroyuki Kaiki, Mizuho Yabushita, Atsushi Fukuoka
    INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH 56 49 14471 - 14478 2017年12月 [査読有り][通常論文]
     
    The catalytic conversion of cellulose to glucose at the industrial scale is a sustainable approach to the production of fuels and chemicals. Herein, we report the hydrolysis of cellulose to glucose using an inexpensive carbon catalyst in a continuous slurry process. A carbon catalyst prepared by air oxidation showed the highest activity for cellulose hydrolysis owing to the large number of weakly acidic functional groups. The air-oxidized carbon catalyst hydrolyzed cellulose in a plug-flow slurry reactor after mix-milling to produce soluble beta-1,4-glucans. Further hydrolysis of the beta-1,4-glucans to glucose was achieved using a fixed-bed reactor containing Amberlyst-70 catalyst in series with the slurry reactor to obtain glucose in 59% yield. Another approach was to use dilute H3PO4 for the hydrolysis of the beta-1,4-glucans to glucose with a 70% yield, resulting in a space time yield of glucose of 456 kg m(-3) h(-1). The simple design, short residence time, and high space time yield will enable the scaleup of this process using existing chemical technology.
  • Abhijit Shrotri, Hirokazu Kobayashi, Atsushi Fukuoka
    Nanoporous Catalysts for Biomass Conversion 79 - 98 2017年09月22日
  • Hirokazu Kobayashi, Atsushi Fukuoka
    JOURNAL OF PHYSICAL CHEMISTRY C 121 32 17332 - 17338 2017年08月 [査読有り][通常論文]
     
    Recognition of saccharides is crucial in their separation, purification, and catalytic conversion. In this work, we demonstrated that hexagonal boron nitride (h-BN) adsorbs saccharides in water. Controlled experiments and density functional theory calculations have indicated that the adsorption is mainly driven by dispersion force occurring between CH groups of saccharides and it electrons on basal plane of h-BN. Accordingly, h-BN can distinguish between different saccharides by the number of CH groups that can contact with the basal plane. The salt effect on the adsorption correlated with the Hofmeister series, which shows the presence of hydrophobic interactions in the adsorption of sugars. Moreover, conversion of glucose to fructose is accelerated by h-BN, possibly due to its acid/base catalysis.
  • Haruka Yokoyama, Hirokazu Kobayashi, Jun-ya Hasegawa, Atsushi Fukuoka
    ACS CATALYSIS 7 7 4828 - 4834 2017年07月 [査読有り][通常論文]
     
    Isomannide is a potential feedstock for the production of super engineering plastics. A prospective route to obtain isomannide is dehydration of mannitol derived from lignocellulosic biomass, but homogeneous acid catalysts reported in the literature produce a large amount of 2,5-sorbitan as a byproduct in the dehydration reaction. In this work, we initially studied the mechanism of proton-induced dehydration of mannitol by density functional theory calculations, which suggested that local steric hindrance around acid sites designed at the angstrom level can tune the selectivity toward isomannide formation. Based on this prediction, we found that the precisely defined microporous confinement offered by H beta provides improved selectivity and high catalytic activity for the production of isomannide, where 1,4-dehydration is favored by 20 kJ mol(-1) of activation energy. The optimization of the Si/Al ratio of H beta to balance the acid amount and hydrophobicity improved the catalytic activity and achieved 63% yield of isomannide, far exceeding the best result reported previously (35% yield).
  • Hirokazu Kobayashi, Kota Techikawara, Atsushi Fukuoka
    GREEN CHEMISTRY 19 14 3350 - 3356 2017年07月 [査読有り][通常論文]
     
    Chitin is the second most abundant biomass and characteristically contains nitrogen atoms in its monomer units. These favourable features promote chitin to be a potential resource for renewable organonitrogen compounds. 2-Acetamido-2-deoxysorbitol (ADS) is an attractive target in the derivatives of chitin, but the conversion of chitin to ADS has not been reported so far. In this work, we demonstrate the catalytic conversion of chitin to ADS using mechanocatalysis in the presence of H2SO4 and subsequent hydrolytic hydrogenation by H2SO4 and Ru/TiO2 without any purification process. Our study clarified that the yield of ADS is strongly influenced by the reaction temperature and pH. The hydrolysis favourably proceeds at high temperature and low pH (2.0), but the hydrogenation needs a low temperature and a specific pH of 3-4 to achieve high selectivity. Specifically, in the hydrogenation step, an acid causes various side-reactions of amide and hemiacetal groups especially in the presence of a Ru catalyst, whereas even a small amount of base drastically accelerates the retro-aldol reaction to form erythritol and N-acetylethanolamine. Therefore, a one-pot but two-step reaction is necessary to optimise both the hydrolysis and hydrogenation steps and maximise the overall yield of ADS up to 52%.
  • Mizuho Yabushita, Peng Li, Timur Islamoglu, Hirokazu Kobayashi, Atsushi Fukuoka, Omar K. Farha, Alexander Katz
    INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH 56 25 7141 - 7148 2017年06月 [査読有り][通常論文]
     
    This manuscript demonstrates the synthesis of selective Lewis-acid sites in a metal organic framework (MOF) for glucose transformation to 5-hydroxymethylfurfural (HMF). These sites are synthesized via partial phosphate modification of zirconia-cluster nodes in MOF NU-1000, which titrates strong Lewis-acid sites that would lead to undesired side reactions. Our Mechanistic study using isotope tracer analysis and kinetic isotope effect measurements reveals that an isomerization dehydration mechanism mainly occurs, on the MOF catalyst, where fructose is an intermediate. This mechanism suggests that dilute concentrations are favorable in order to suppress undesired intermorecul condensation of glucose/fructose/HMT and maximize HMF yield. We demonstrate both high yield and selectivity of HMF formation of 64% with the MOF catalyst, at an initial glucose concentration of 1 mM in water/2-propanol. In stark contrast similar partial phosphate modification of a bulk zirconia yields a catalyst that exhibits poor HMF selectivity, while possessing nearly identical Bronsted acidity to the selective NU-1000-based catalyst.
  • Mizuho Yabushita, Peng Li, Kathleen A. Durkin, Hirokazu Kobayashi, Atsushi Fukuoka, Omar K. Farha, Alexander Katz
    LANGMUIR 33 17 4129 - 4137 2017年05月 [査読有り][通常論文]
     
    The molecular origins of adsorption of lignin-derived phenolics to metalorganic framework NU-1000 are investigated from aqueous solution as well as in competitive mode with glucose present in the same aqueous mixture. A comparison of adsorption equilibrium constants (K-ads) for phenolics functionalized with either carboxylic acid or aldehyde substituents demonstrated only a slight increase (less than a factor of 6) for the former according to both experiments and calculations. This small difference in K-ads between aldehyde and carboxylic-acid substituted adsorbates is consistent with the pyrene unit of NU-1000 as the adsorption site, rather than the zirconia nodes, while at saturation coverage, the adsorption capacity suggests multiple guests per pyrene. Experimental standard free energies of adsorption directly correlated with the molecular size and electronic structure calculations confirmed this direct relationship, with the pyrene units as adsorption site. The underlying origins of this relationship are grounded in noncovalent pi-pi interactions as being responsible for adsorption, the same interactions present in the condensed phase of the phenolics, which to a large extent govern their heat of vaporization. Thus, NU-1000 acts as a preformed aromatic cavity for driving aromatic guest adsorption from aqueous solution and does so specifically without causing detectable glucose adsorption from aqueous solution, thereby achieving complete glucosephenolics separations. The reusability of NU-1000 during an adsorption/desorption cycle was good, even with some of the phenolic compounds with greatest affinity not easiliy removed with water and ethanol washes at room temperature. A competitive adsorption experiment gave an upper bound for K-ads for glucose of at most 0.18 M-1, which can be compared with K-ads for the phenolics investigated here, which fell in the range of 443-42 639 M-1. The actual value of K-ads for glucose may be much closer to zero given the lack of observed glucose uptake with NU-1000 as adsorbent.
  • 金属触媒を用いたセルロースからの糖アルコール生成
    小林広和, 福岡淳
    化学工学 81 4 187 - 189 2017年04月 [査読有り][招待有り]
  • Navneet Kumar Gupta, Atsushi Fukuoka, Kiyotaka Nakajima
    ACS CATALYSIS 7 4 2430 - 2436 2017年04月 [査読有り][通常論文]
     
    Aqueous-phase dehydration of xylose into furfural was studied in the presence of amorphous Nb2O5 with water-compatible Bronsted and Lewis acid sites. Nb2O5 was determined as a more active and selective catalyst for xylose dehydration than typical homogeneous Bronsted and Lewis acid catalysts including HCl and Sc(OTf)(3), and Nb2O5 converted 93% of xylose with 48% selectivity toward furfural in water at 393 K. No significant loss of the original catalytic activity was observed after Nat-exchange treatment, which indicates that the reaction proceeded only on Lewis acid sites. Isotope-labeling experiments using D2O and xylose suggested that furfural is formed through stepwise dehydration via a highly reactive dicarbonyl intermediate on Nb2O5, whereas typical Lewis acids such as CrCl3 and Sc(OTf)(3), convert xylose to furfural in water through hydride transfer and subsequent dehydration via xylulose as a ketose-type intermediate. The difference in the reaction mechanism accounts for the lower activation energy (83 kJ mol(-1)) with Nb2O5 than those with Sc(OTf)(3) and HCl (107-131 kJ mol(-1)). Continuous extraction of evolved furfural with toluene enabled a large increase in the selectivity toward furfural from 48% to 72% and prevented deactivation of the Lewis acid sites by covering with heavy byproducts, represented by humin.
  • Hirokazu Kobayashi, Shogo Ito, Kenji Hara, Atsushi Fukuoka
    CHINESE JOURNAL OF CATALYSIS 38 3 420 - 425 2017年03月 [査読有り][通常論文]
     
    A mesoporous sulfated zirconia-silica catalyst bearing only Bronsted acid sites converted glycerol to acrolein in 81% yield with 82% selectivity. Space time yield as high as 9.0 mmol h(-1) g(cat)(-1) was achieved even at a low reaction temperature of 523 K. The catalytic activity and selectivity were higher than those of typical sulfated zirconia. It is proposed that the milder acidity due to dilution of zirconium species by silica and large pore size for faster diffusion contributed towards the better catalytic performance. (C) 2016, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.
  • 小林広和, 福岡淳
    硫酸と工業 70 1 11‐18  2017年01月15日 [査読無し][通常論文]
  • 中島清隆, 福岡淳
    ペトロテック 40 1 25‐29  2017年01月01日 [査読無し][通常論文]
  • 中島清隆, 福岡淳
    セラミックス 52 1 6‐10  2017年01月01日 [査読無し][通常論文]
  • Abhijit Shrotri, Hirokazu Kobayashi, Atsushi Fukuoka
    Advances in Catalysis 60 1 - 57 2017年 [査読有り][通常論文]
     
    Lignocellulose and chitin are the two most abundant renewable sources of organic carbon available as alternative for chemical and fuel synthesis. Catalytic conversion of these composite polymers to monomers is a multifaceted challenge. Lignocellulose and chitin are inherently unreactive toward chemical attacks as they serve the function of structural materials in plants and animals. A combination of pretreatment and catalytic reaction is necessary to convert these materials into useful small molecules. These upstream reactions involving depolymerization of polymers are the roadblock for realizing future chemicals production based on biomass. In this chapter, we first discuss the pretreatment technologies currently available for lignocellulose and their relevance for catalytic conversion. Catalytic pathways for depolymerization of cellulose, hemicellulose, and lignin are then discussed, highlighting important reactions and mechanism. An analogy is derived between mechanism of cellulose hydrolysis using enzymes and heterogeneous carbon catalysts containing acidic functional groups. Finally, the use of chitin as a renewable carbon source is discussed. The chemical structure of chitin is described along with its origin from crab shells and availability. Recent advances in conversion of chitin to N-acetylglucosamine and its derivatives are described.
  • Mizuho Yabushita, Kota Techikawara, Hirokazu Kobayashi, Atsushi Fukuoka, Alexander Katz
    ACS SUSTAINABLE CHEMISTRY & ENGINEERING 4 12 6844 - 6851 2016年12月 [査読有り][通常論文]
     
    This manuscript quantitatively investigates the effect of weak acid site surface density on adsorption and catalytic hydrolysis of long-chain beta-glucans, with post-synthetically modified zeolite-templated carbon (ZTC) catalysts. Our approach requires ZTC-surface modification and overcomes previous limitations of pore collapse in accomplishing this, which has previously necessitated electrochemical methods. We demonstrate that mild ZTC treatment in hydrogen peroxide preserves the 1.1 nm micropores of ZTC, which were previously shown to be ideal for beta-glucan adsorption, while synthesizing surface-modified ZTC catalysts that hydrolyze adsorbed beta glucans to glucose in up to 87% yield. Our results demonstrate a direct increase in catalytic hydrolysis activity and glucose yield upon increasing acid site density via surface functionalization. Upon investigating the mechanism of catalytic hydrolysis under buffered conditions, we rule out the synthesis of acid sites with stronger acidity as a result of possible greater anion delocalization as well as the possibility of a cooperative acid base bifunctional mechanism. Our data instead argue for the importance of a high density of surface carboxylic acid functionality as promoting the likelihood of pairing a surface acid site with a glycosidic oxygen of an adsorbed glucan on a length scale that is commensurate with that required for general acid catalysis. From this perspective, our ZTC catalysts function much like zeolites wherein both achieve high rates with weak-acid sites by coupling adsorption of reactant into a confined domain containing the acid site, and general-acid catalyzed reaction.
  • Abhijit Shrotri, Hirokazu Kobayashi, Atsushi Fukuoka
    CHEMSUSCHEM 9 11 1299 - 1303 2016年06月 [査読有り][通常論文]
     
    Oxygenated carbon catalyzes the hydrolysis of cellulose present in lignocellulosic biomass by utilizing the weakly acidic functional groups on its surface. Here we report the synthesis of a biomimetic carbon catalyst by simple and economical air-oxidation of a commercially available activated carbon. Air- oxidation at 450-500 degrees C introduced 2000-2400molg(-1) of oxygenated functional groups on the material with minor changes in the textural properties. Selectivity towards the formation of carboxylic groups on the catalyst surface increased with the increase in oxidation temperature. The degree of oxidation on carbon catalyst was found to be proportional to its activity for hydrolysis of cellulose. The hydrolysis of eucalyptus in the presence of carbon oxidized at 475 degrees C afforded glucose yield of 77% and xylose yield of 67%.
  • Nobuhiro Ishito, Kenji Hara, Kiyotaka Nakajima, Atsushi Fukuoka
    JOURNAL OF ENERGY CHEMISTRY 25 2 306 - 310 2016年03月 [査読有り][通常論文]
     
    Thermal decomposition of formic acid on SiO2, CeO2 and gamma-Al2O3 was studied as an elementary step of reverse water-gas shit reaction (RWGS) over supported Au catalysts. gamma-Al2O3 showed the highest CO selectivity among the tested oxides in the decomposition of formic acid. Infrared spectroscopy showed the formation of four formate species on gamma-Al2O3: three eta(1)-type and one mu(2)-type species, and these formates decomposed to CO at 473 K or higher. Au-loaded gamma-Al2O3 samples were prepared by a deposition precipitation method and used as catalysts for RWGS. The supported Au catalyst gave CO with high selectivity over 99% from CO2 and H-2, which is attributed to the formation of formates on Au and subsequent decomposition to CO on gamma-Al2O3. (C) 2015 Science Press and Dalian Institute of Chemical Physics. All rights reserved.
  • Abhijit Shrotri, Hirokazu Kobayashi, Atsushi Fukuoka
    CHEMCATCHEM 8 6 1059 - 1064 2016年03月 [査読有り][通常論文]
     
    A carbon catalyst containing a high density of carboxyl groups was prepared by solvent-free mechanochemical oxidation of activated carbon by using persulfate salts as the oxidant. The mechanochemical oxidation preferentially oxidized the carbon to introduce carboxyl groups without incorporation of sulfonated groups. The material exhibited hydrophilic behavior and was easily dispersed in water. Upon mix-milling, the oxidized carbon showed good catalytic activity for the hydrolysis of cellulose, even at a low catalyst loading. Glucose was obtained in 85% yield from mix-milled cellulose in the presence of a trace amount of HCl after a reaction time of 20min.
  • Shino Sato, Kotaro Namba, Kenji Hara, Atsushi Fukuoka, Kei Murakoshi, Kohei Uosaki, Katsuyoshi Ikeda
    JOURNAL OF PHYSICAL CHEMISTRY C 120 4 2159 - 2165 2016年02月 [査読有り][通常論文]
     
    Electrocatalytic model surfaces consisting of catalytically active local surface sites and conducting electrode were formed by layer by-layer assembly of functional molecules. The strength of electronic coupling between the catalytic surface sites and the electrode was tuned by changing the length and structure of wire molecules. When cobalt(II) tetraphenylporphyrin was employed as a model surface site, the induced activity for oxygen reduction reaction was critically dependent on the coupling strength through the wire molecules. The overall reaction kinetics was disentangled to contributions of the internal electron tunneling and the intermolecular electron transfer. In the weak coupling condition with nanometer separation between the porphyrin and electrode, the overall reaction rate was limited by coherent quantum tunneling rate inside the catalytic system. In the strong coupling condition with the closer separation, on the other hand, the activity of the catalytic sites was significantly suppressed, and the electrochemical charge transfer rate was thus rate-limiting. This result provides a detailed insight for molecular -scale design methodology of highly efficient electrocatalysts.
  • Mizuho Yabushita, Peng Li, Varinia Bernales, Hirokazu Kobayashi, Atsushi Fukuoka, Laura Gagliardi, Omar K. Farha, Alexander Katz
    CHEMICAL COMMUNICATIONS 52 44 7094 - 7097 2016年 [査読有り][通常論文]
     
    Metal-organic framework (MOF) material NU-1000 adsorbs dimers cellobiose and lactose from aqueous solution, in amounts exceeding 1250 mg g(NU-1000)(-1) while completely excluding the adsorption of the monomer glucose, even in a competitive mode with cellobiose. The MOF also discriminates between dimers consisting of alpha and beta linkages, showing no adsorption of maltose. Electronic structure calculations demonstrate that key to this selective molecular recognition is the number of favorable CH-pi interactions made by the sugar with pyrene units of the MOF.
  • Mizuho Yabushita, Peng Li, Hirokazu Kobayashi, Atsushi Fukuoka, Omar K. Farha, Alexander Katz
    CHEMICAL COMMUNICATIONS 52 79 11791 - 11794 2016年 [査読有り][通常論文]
     
    Metal-organic framework NU-1000 selectively adsorbs furanics, while completely excluding the adsorption of monomeric sugars from the same aqueous mixture. The highly refined degree of molecular recognition exhibited by NU-1000 is exemplified with it selectively adsorbing 5-hydroxymethylfurfural, even in the presence of up to a 300-fold excess of glucose in solution.
  • Hirokazu Kobayashi, Hiroyuki Kaiki, Abhijit Shrotri, Kota Techikawara, Atsushi Fukuoka
    CHEMICAL SCIENCE 7 1 692 - 696 2016年 [査読有り][通常論文]
     
    Biomass is the sole carbon-based renewable resource for sustaining the chemical and fuel demands of our future. Lignocellulose, the primary constituent of terrestrial plants, is the most abundant non-food biomass, and its utilisation is a grand challenge in biorefineries. Here we report the first reusable and cost-effective heterogeneous catalyst for the depolymerisation of lignocellulose. Air oxidation of woody biomass (Eucalyptus) provides a carbonaceous material bearing an aromatic skeleton with carboxylic groups (2.1 mmol g(-1)) and aliphatic moieties. This catalyst hydrolyses woody biomass (Eucalyptus) to sugars in high yields within 1 h in trace HCl aq. Furthermore, after the reaction, the solid residue composed of the catalyst and insoluble ingredients of woody biomass is easily transformed back to fresh catalyst by the same air oxidation method. This is a self-contained system using woody biomass as both the catalyst source and substrate for realising facile catalyst preparation and recycling.
  • Mizuho Yabushita, Peng Li, Hirokazu Kobayashi, Atsushi Fukuoka, Omar K. Farha, Alexander Katz
    Chemical Communications 52 79 11791 - 11794 Royal Society of Chemistry ({RSC}) 2016年 [査読有り][通常論文]
     
    Metal-organic framework NU-1000 selectively adsorbs furanics, while completely excluding the adsorption of monomeric sugars from the same aqueous mixture. The highly refined degree of molecular recognition exhibited by NU-1000 is exemplified with it selectively adsorbing 5-hydroxymethylfurfural, even in the presence of up to a 300-fold excess of glucose in solution.
  • 中島清隆, 福岡淳
    ゼオライト 32 4 113 - 121 ゼオライト学会 2015年12月10日 [査読無し][通常論文]
  • Po-Wen Chung, Mizuho Yabushita, Anh The To, YounJue Bae, Joseph Jankolovits, Hirokazu Kobayashi, Atsushi Fukuoka, Alexander Katz
    ACS Catalysis 5 11 6422 - 6425 2015年11月 [査読有り][通常論文]
     
    We demonstrate adsorption and depolymerization of long-chain beta-glu strands derived from cellulose, within the microporous confines of a zeolite-templated carbon (ZTC) material. The ZTC adsorbs beta-glu strands that have a radius of gyration several-fold larger than the ZTC micropore diameter and do so rapidly (less than 2 min) and in adsorbed beta-glu coverages of up to 80% of the ZTC mass. Principles of supramolecular chemistry predict that such adsorption occurs inside of the ZTC based on its micropore size as host being nearly ideal for glucan guest. A comparative study of partially etched materials and nitrogen physisorption at -196 degrees C indeed demonstrates beta-glu adsorption to occur within internal ZTC micropores rather than on the external surface. Such adsorption under micropore confinement is expected to place significant mechanical strain on the beta-glu strand, and this strain can be in principle relieved by depolymerization via hydrolysis. This hypothesis motivated us to investigate depolymerization of adsorbed beta-glu strands in ZTC, where the ZTC serves as a catalyst for adsorbed beta-glu hydrolysis. After a 3 h treatment in water at 180 degrees C, adsorbed beta-glu was converted to soluble glucose in 73% yield. This represents the highest glucose yield observed to date for a carbon catalyst without postsynthetic surface functionalization and speaks to the effectiveness of weak-acid sites for beta-glu hydrolysis within a constrained micropore environment.
  • Mizuho Yabushita, Hirokazu Kobayashi, Kyoichi Kuroki, Shogo Ito, Atsushi Fukuoka
    CHEMSUSCHEM 8 22 3760 - 3763 2015年11月 [査読有り][通常論文]
     
    Chitin, a polymer of N-acetylglucosamine units with -1,4-glycosidic linkages, is the most abundant marine biomass. Chitin monomers containing N-acetyl groups are useful precursors to various fine chemicals and medicines. However, the selective conversion of robust chitin to N-acetylated monomers currently requires a large excess of acid or a long reaction time, which limits its application. We demonstrate a fast catalytic transformation of chitin to monomers with retention of N-acetyl groups by combining mechanochemistry and homogeneous catalysis. Mechanical-force-assisted depolymerization of chitin with a catalytic amount of H2SO4 gave soluble short-chain oligomers. Subsequent hydrolysis of the ball-milled sample provided N-acetylglucosamine in 53% yield, and methanolysis afforded 1-O-methyl-N-acetylglucosamine in yields of up to 70%. Our process can greatly reduce the use of acid compared to the conventional process.
  • Nobuhiro Ishito, Hirokazu Kobayashi, Kiyotaka Nakajima, Yoshifumi Maegawa, Shinji Inagaki, Kenji Hara, Atsushi Fukuoka
    CHEMISTRY-A EUROPEAN JOURNAL 21 44 15564 - 15569 2015年10月 [査読有り][通常論文]
     
    Periodic mesoporous organosilica (PMO) is a unique material that has a crystal-like wall structure with coordination sites for metal complexes. A Ru complex, [RuCl2(CO)(3)](2), is successfully immobilized onto 2,2'-bipyridine (BPy) units of PMO to form a single-site catalyst, which has been confirmed by various physicochemical analyses. Using NaClO as an oxidant, the Ru-immobilized PMO oxidizes the tertiary CH bonds of adamantane to the corresponding alcohols at 57 times faster than the secondary CH bonds, thereby exhibiting remarkably high regioselectivity. Moreover, the catalyst converts cis-decalin to cis-9-decalol in a 63% yield with complete retention of the substrate stereochemistry. The Ru catalyst can be separated by simple filtration and reused without loss of the original activity and selectivity for the oxidation reactions.
  • Nobuhiro Ishito, Hirokazu Kobayashi, Kiyotaka Nakajima, Yoshifumi Maegawa, Shinji Inagaki, Kenji Hara, Atsushi Fukuoka
    CHEMISTRY-A EUROPEAN JOURNAL 21 44 15564 - 15569 2015年10月 [査読有り][通常論文]
     
    Periodic mesoporous organosilica (PMO) is a unique material that has a crystal-like wall structure with coordination sites for metal complexes. A Ru complex, [RuCl2(CO)(3)](2), is successfully immobilized onto 2,2'-bipyridine (BPy) units of PMO to form a single-site catalyst, which has been confirmed by various physicochemical analyses. Using NaClO as an oxidant, the Ru-immobilized PMO oxidizes the tertiary CH bonds of adamantane to the corresponding alcohols at 57 times faster than the secondary CH bonds, thereby exhibiting remarkably high regioselectivity. Moreover, the catalyst converts cis-decalin to cis-9-decalol in a 63% yield with complete retention of the substrate stereochemistry. The Ru catalyst can be separated by simple filtration and reused without loss of the original activity and selectivity for the oxidation reactions.
  • Hirokazu Kobayashi, Mizuho Yabushita, Atsushi Fukuoka
    Reaction Pathways and Mechanisms in Thermocatalytic Biomass Conversion I: Cellulose Structure, Depolymerization and Conversion by Heterogeneous Catalysts 15 - 26 2015年09月25日 [査読有り][通常論文]
     
    Efficient hydrolysis of cellulosic biomass to glucose is a grand challenge for the realization of a nonfood biorefinery. In recent years, solid catalysts have attracted significant attention for biomass conversion, as they can be separated from product solutions and their functions can be designed. In this chapter, we describe activated carbons that can hydrolyze cellulose and real biomass to glucose in yields up to 88 % in the presence of a trace amount of hydrochloric acid. Creating contacts between the solid catalyst and the solid substrate by ball-milling is the key to realizing the potential of this catalytic system. Activated carbon adsorbs cellulosic molecules by van der Waals forces, CH-Π hydrogen bonds, and hydrophobic interactions between the polyaromatic surface of the carbon and the axial planes of glucans, namely, hydrophobic groups. Subsequently, the weakly acidic groups of the carbon surface such as carboxylic acids cleave the glycosidic bonds of cellulose via oxocarbenium intermediates, for which the salicylic acid structure is especially effective.
  • Hirokazu Kobayashi, Mizuho Yabushita, Jun-ya Hasegawa, Atsushi Fukuoka
    JOURNAL OF PHYSICAL CHEMISTRY C 119 36 20993 - 20999 2015年09月 [査読有り][通常論文]
     
    Carbon materials bearing carboxylic acids and phenolic groups efficiently catalyze the hydrolysis of cellulose. In this work, we demonstrate that salicylic acid and phthalic acid show higher activity than other substituted benzoic acids as models of catalytic sites on carbons in the hydrolysis of cellobiose and cellulose. Notably, their turnover frequencies are larger than those of o-chlorobenzoic acid and o-trifluoromethylbenzoic acid, despite their lower acid strength. The high catalytic performance of salicylic acid and phthalic acid is not attributed to a reduction of activation energy but to an increase in the frequency factor. Nuclear magnetic resonance and density functional theory studies indicate that one oxygenated group forms a hydrogen bond with a hydroxyl group in cellobiose, which boosts the probability of attack of the neighboring carboxylic acid on the glycosidic bond. The computation also predicts a hydrolysis mechanism including an S(N)1 reaction with anomeric inversion, which reasonably accounts for the experimental results in the conversion of cellobiose.
  • Mizuho Yabushita, Hirokazu Kobayashi, Abhijit Shrotri, Kenji Hara, Shogo Ito, Atsushi Fukuoka
    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 88 7 996 - 1002 2015年07月 [査読有り][通常論文]
     
    1,4-Sorbitan is a precursor to environmentally benign surfactants, which can be produced from biomass via sorbitol. Currently, sulfuric acid-catalyzed dehydration of sorbitol is the most widely used route for industrial synthesis of 1,4-sorbitan. In this work, we have studied the mechanism of the sorbitol dehydration by sulfuric acid. Our results show that both thermodynamic and kinetic parameters play significant roles to determine the yield of 1,4-sorbitan. Sorbitol preferentially forms an adduct with sulfuric acid, thereby inhibiting the subsequent dehydration of 1,4-sorbitan to isosorbide. Furthermore, a reaction mechanism is proposed for the dehydration reaction, which involves an S(N)2 reaction on primary C1 of sorbitol attacked by OH of secondary C4.
  • 小林 広和, 福岡 淳
    石油学会 年会・秋季大会講演要旨集 2015 113 - 113 公益社団法人 石油学会 2015年 
    リグノセルロースは最も豊富に存在する非可食バイオマスであり、化学資源としての利用が期待される。我々は、含酸素官能基を持つ炭素がセルロースの加水分解触媒として高い活性を示すことを見出した。炭素表面の芳香族はセルロースを強く吸着し、酸素官能基はグリコシド結合の加水分解の活性点として機能する。また、セルロースと類似構造をもつキチンの分解を達成した。触媒は硫酸であるが、メカノキャタリシスと加メタノール分解を用いることにより、酸使用量を従来法の0.2 %に低減した。
  • Hirokazu Kobayashi, Haruka Yokoyama, Bo Feng, Atsushi Fukuoka
    GREEN CHEMISTRY 17 5 2732 - 2735 2015年 [査読有り][通常論文]
     
    Conversion of sorbitol to isosorbide by heterogeneous catalysts is a challenge in biorefinery. Herein, H-beta zeolites with specific Si/Al ratios uniquely give isosorbide in up to 76% yield under mild conditions. Mechanistic study has suggested that acid sites on hydrophobic internal surface are active for this reaction.
  • Hirokazu Kobayashi, Haruka Yokoyama, Bo Feng, Atsushi Fukuoka
    GREEN CHEMISTRY 17 5 2732 - 2735 2015年 [査読有り][通常論文]
     
    Conversion of sorbitol to isosorbide by heterogeneous catalysts is a challenge in biorefinery. Herein, H-beta zeolites with specific Si/Al ratios uniquely give isosorbide in up to 76% yield under mild conditions. Mechanistic study has suggested that acid sites on hydrophobic internal surface are active for this reaction.
  • Hirokazu Kobayashi, Haruka Yokoyama, Bo Feng, Atsushi Fukuoka
    GREEN CHEMISTRY 17 5 2732 - 2735 2015年 [査読有り][通常論文]
     
    Conversion of sorbitol to isosorbide by heterogeneous catalysts is a challenge in biorefinery. Herein, H-beta zeolites with specific Si/Al ratios uniquely give isosorbide in up to 76% yield under mild conditions. Mechanistic study has suggested that acid sites on hydrophobic internal surface are active for this reaction.
  • Shrotri Abhijit, 小林 広和, 福岡 淳
    Journal of the Japan Petroleum Institute 58 1 1 - 8 The Japan Petroleum Institute 2015年01月 [査読有り][通常論文]
     
    機械的な処理によってセルロースの加水分解反応性を高める研究が盛んに行われてきた。本稿では,最新の混合粉砕とメカノキャタリシスを利用したセルロース分解を紹介する。まず,混合粉砕に関し,セルロースと弱酸性官能基を持つ活性炭触媒とを一緒に粉砕すると,両者の間に強い接触が形成される。この試料を加水分解反応に供すると,単独粉砕の場合に比べて13倍の速度でセルロースが加水分解されるが,生成するグルコースの逐次分解は混合粉砕の影響を受けない。つまり,固体─固体反応を選択的に加速できる。その結果,グルコース収率88 %を達成できる。さらに,本法はセルロースの加水分解水素化反応にも適用でき,水素圧9気圧の温和な条件下でも糖アルコール収率は68 %に達する。一方,メカノキャタリシスでは強酸を添加して粉砕することにより,セルロースが加水分解されて可溶性のオリゴ糖に転化する。このオリゴ糖を移動水素化条件で分解すると糖アルコールが収率90 %で得られる。また,可溶性であるため流通系にも容易に適用できる。
  • Hara K, Kobayashi H, Komanoya T, Huang S.-J, Pruski M, Fukuoka A
    RSC Green Chemistry 2015-January 33 61 - 76 2015年 [査読有り][通常論文]
  • Kobayashi H, Ohta H, Fukuoka A
    RSC Energy and Environment Series 2015-January 13 52 - 73 2015年 [査読有り][通常論文]
  • C. Jiang, K. Hara, K. Namba, H. Kobayashi, S. Ittisanronnachai, H. Nishihara, T. Kyotoni, A. Fukuoka
    Chemistry Letters 43 11 1794 - 1796 Chemical Society of Japan 2014年11月05日 [査読有り][通常論文]
     
    © 2014 The Chemical Society of Japan. Zeolite-templated carbon (ZTC) was utilized to prepare Pt nanoparticles as a support by using a simple impregnation method. The choice of a cationic Pt precursor led to the formation of highly and uniformly dispersed Pt nanoparticles on ZTC, which afforded high conversion in the catalytic hydrogenation of phenylacetylene.
  • Chuanxia Jiang, Kenji Hara, Kotaro Namba, Hirokazu Kobayashi, Somlak Ittisanronnachai, Hirotomo Nishihara, Takashi Kyotani, Atsushi Fukuoka
    Chemistry Letters 43 11 1794 - 1796 Chemical Society of Japan 2014年11月 [査読有り][通常論文]
     
    Zeolite-templated carbon (ZTC) was utilized to prepare Pt nanoparticles as a support by using a simple impregnation method. The choice of a cationic Pt precursor led to the formation of highly and uniformly dispersed Pt nanoparticles on ZTC, which afforded high conversion in the catalytic hydrogenation of phenylacetylene.
  • Ying Shi, Yuta Nabae, Teruaki Hayakawa, Hirokazu Kobayashi, Mizuho Yabushita, Atsushi Fukuoka, Masa-aki Kakimoto
    POLYMER JOURNAL 46 10 722 - 727 2014年10月 [査読有り][通常論文]
     
    A new type of hyperbranched aromatic poly(ether ketone) terminated with carboxylic acid groups (P2) was synthesized via a one-step polycondensation of a symmetric AB(2) monomer, 4,4 '-(m-phenylenedioxy)-bis(benzenecarboxylic acid), using phosphorous pentoxide-methanesulfonic acid (PPMA) as a condensing agent and solvent. Subsequently, the terminal carboxylic acid functional group of P2 was converted to an ethyl ester functional group by treatment with thionyl chloride followed by ethanol in the presence of triethylamine. The weight-average molecular weight (M-w) of the ethyl ester-terminated hyperbranched poly(ether ketone) (P3) was measured by gel permeation chromatography. By changing the reaction time and the amount of PPMA, Mw can be controlled in the range of 4.2 x 10(4) to 1.6 x 10(5). P2 was soluble in polar solvents, and P3 was soluble in less-polar solvents. The thermal stabilities of the poly(ether ketone)s were investigated using thermogravimetric analysis, which indicated that the decompositions of P2 and P3 start at around 150 and 200 C-circle, respectively. The inherent viscosities of P2 were in the range of 0.101-0.171, while those P3 ranged from 0.067 to 0.112. The ion exchange capacities calculated by titration were in the range of 2.2-2.8 mol kg (-1) according to the difference in molecular weights. P2 was tested as a weak-acid catalyst and exhibited a certain catalytic activity for the hydrolysis of cellulose to glucose.
  • Hidetoshi Ohta, Bo Feng, Hirokazu Kobayashi, Kenji Hara, Atsushi Fukuoka
    CATALYSIS TODAY 234 139 - 144 2014年10月 [査読有り][通常論文]
     
    Bimetallic Pt-Re/ZrO2 catalysts were developed for the selective hydrodeoxygenation of 4-propylphenol as a lignin model to n-propylbenzene in water. The addition of Re to Pt/ZrO2 improved the catalyst stability and product selectivity. Reaction temperature greatly affected not only reaction efficiency but also product distribution. n-Propylbenzene was obtained in up to 73% yield with ca. 80% selectivity. After the reaction, the catalyst was deactivated possibly due to water-induced wrapping of Pt nanoparticles in ZrO2. The reaction may involve the hydrogenation of 4-propylphenol to 4-propylcyclohexanol, followed by the dehydration to give 4-propylcyclohexene and the subsequent dehydrogenation to n-propylbenzene. (C) 2014 Elsevier B.V. All rights reserved.
  • Kenji Hara, Masaya Sawamura, Atsushi Fukuoka
    CHEMICAL RECORD 14 5 869 - 878 2014年10月 [査読有り][通常論文]
     
    Catalysts are one of the key materials for realizing a sustainable society. However, we may encounter problematic cases where conventional catalyst systems cannot provide effective solutions. We thus believe that the establishment of novel methods of catalyst preparation is currently necessary. Utilization of high-density monolayers of molecular metal complexes is our strategy, and we expect that this methodology will enable facile and systematic screening of unique and efficient catalysts. This Personal Account describes our challenges to establish such an immature method in catalyst preparation as well as the related background and perspective. Preparation and catalysis by high-density monolayers of Rh complexes with N-heterocyclic carbene, structurally compact phosphine and diisocyanide ligands on gold surfaces are presented. The catalytic application of a high-density Pd-bisoxazoline complex prepared on a single-crystal silicon surface is also shown. Uniquely high catalyst turnover numbers and high chemoselectivities were observed with these catalyst systems.
  • Aritomo Yamaguchi, Osamu Sato, Naoki Mimura, Yoshihiko Hirosaki, Hirokazu Kobayashi, Atsushi Fukuoka, Masayuki Shirai
    CATALYSIS COMMUNICATIONS 54 22 - 26 2014年09月 [査読有り][通常論文]
     
    Softwood chips have been directly converted into sugar alcohols by supported platinum catalysts in water without any acid catalysts. The cellulose and hemicellulose in the wood chips were converted with 94% conversion and 62% yield and the lignin remained as solid after the reaction. (C) 2014 Elsevier B.V. All rights reserved.
  • Jose Isagani B. Janairo, Tatsuya Sakaguchi, Kenji Hara, Atsushi Fukuoka, Kazuyasu Sakaguchi
    CHEMICAL COMMUNICATIONS 50 66 9259 - 9262 2014年08月 [査読有り][通常論文]
     
    Highly branched, coral-like Pd nanostructures were formed using a biomineralization peptide conjugated to an oligomeric peptide that simultaneously controls the spatial orientation, arrangement and valency. The Pd nanocoral showed very high catalytic activity in the reduction of nitrophenol. The results highlight the importance of topological arrangement in nanostructure formation and catalytic activity.
  • Jose Isagani B. Janairo, Tatsuya Sakaguchi, Kenji Hara, Atsushi Fukuoka, Kazuyasu Sakaguchi
    CHEMICAL COMMUNICATIONS 50 66 9259 - 9262 2014年08月 [査読有り][通常論文]
     
    Highly branched, coral-like Pd nanostructures were formed using a biomineralization peptide conjugated to an oligomeric peptide that simultaneously controls the spatial orientation, arrangement and valency. The Pd nanocoral showed very high catalytic activity in the reduction of nitrophenol. The results highlight the importance of topological arrangement in nanostructure formation and catalytic activity.
  • Bo Feng, Hirokazu Kobayashi, Hidetoshi Ohta, Atsushi Fukuoka
    JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL 388 41 - 46 2014年07月 [査読有り][通常論文]
     
    Aqueous-phase hydrodeoxygenation of 4-propylphenol as a lignin model to n-propylbenzene was carried out over various Ni based catalysts. Among the catalysts tested, Re-Ni/ZrO2 showed the best catalytic performance. Addition of Re decreased the Ni particle size and greatly improved the catalytic activity. H-2 pressure, Re to Ni ratio and reaction temperature were tuned in the optimization of reaction conditions for favorable formation of n-propylbenzene. Under the conditions of 300 degrees C and 4 MPa H-2, the yield of n-propylbenzene reached 54% over Re-Ni/ZrO2 (Re/Ni ratio 0.33) catalyst. It is suggested that the formation of n-propylbenzene proceeds via the hydrogenation of 4-propylphenol to form 4-propylcyclohexanol, followed by the dehydration to give 4-propylcyclohexene and the subsequent dehydrogenation to n-propylbenzene. (C) 2013 Elsevier B.V. All rights reserved.
  • Mizuho Yabushita, Hirokazu Kobayashi, Jun-ya Hasegawa, Kenji Hara, Atsushi Fukuoka
    CHEMSUSCHEM 7 5 1443 - 1450 2014年05月 [査読有り][通常論文]
     
    Carbon-based materials have attracted interest as high-performance catalysts for the aqueous-phase conversion of cellulose. The adsorption of -glucans plays a crucial role in the catalytic performance of carbons, although the primary driving force and details of the adsorption process remain unclear. This study demonstrates that adsorption occurs at hydrophobic sites on the carbon surface and that hydrophilic groups are not involved. Analysis of adsorption temperature dependence also reveals that the entropy change associated with adsorption is positive. Our results indicate that adsorption occurs by entropically driven hydrophobic interactions in addition to CH- hydrogen bonding. These same CH- hydrogen bonds are also confirmed by DFT calculations. The adsorption of -glucans on carbons is significantly stronger than the affinity between -glucans. The adsorption equilibrium constants of -glucans on carbons increase exponentially with increasing degrees of polymerization, which supports the theory of strong interactions between the carbon and the long -glucans found in cellulose.
  • Abhijit Shrotri, Hirokazu Kobayashi, Akshat Tanksale, Atsushi Fukuoka, Jorge Beltramini
    CHEMCATCHEM 6 5 1349 - 1356 2014年05月 [査読有り][通常論文]
     
    Ru supported on activated carbon was found to be active for the transfer hydrogenation of cellulose oligomers, which were produced by the milling of acidulated microcrystalline cellulose. A C-6 sugar alcohol yield of 85% was obtained in less than 1h reaction time in a batch reactor. Optimum reaction conditions for transfer hydrogenation were determined as 180 degrees C and a pH above 2.2 using glucose as a substrate. Use of deuterium as a marker established that direct transfer of hydride species from 2-propanol to glucose occurs through the dihydride mechanism. Formation of molecular hydrogen from 2-propanol dehydrogenation was found to be a side reaction, with little influence on the glucose hydrogenation step. Conversion of cellulose oligomers to hexitols was also achieved in a continuous flow fixed-bed reactor with 36.4% yield at a liquid hourly space velocity of 4.7h(-1). The catalytic activity did not decrease even after 12h of the onstream reaction.
  • Hirokazu Kobayashi, Yukiyasu Yamakoshi, Yuto Hosaka, Mizuho Yabushita, Atsushi Fukuoka
    CATALYSIS TODAY 226 204 - 209 2014年05月 [査読有り][通常論文]
     
    The influence of lignin and inorganic salts on the catalytic activity was studied in the hydrolytic hydrogenation of real biomass by a supported Pt catalyst. The direct conversion of raw silver grass by Pt/carbon catalyst under H-2 pressure produced small amounts of sorbitol (2.8 wt%), xylitol (7.3 wt%), and other sugar alcohols. It has been suggested that lignin reduces the reactivity of cellulose, as lignin exists together with cellulose in the biomass and both compounds are insoluble in water. Moreover, even weak bases drastically change the product distribution with more by-products such as EG and PG. Bases enhance the decomposition of sugar intermediates and sorbitol. The removal of lignin and inorganic salts by alkaliexplosion and neutralization raises the contents of cellulose and hemicellulose, thus increasing the yields of sorbitol (13 wt%) and xylitol (14 wt%) in the hydrolytic hydrogenation reactions. (C) 2013 Elsevier B.V. All rights reserved.
  • 原賢二, 福岡淳
    化学と生物 52 4 208 - 209 Japan Society for Bioscience, Biotechnology, and Agrochemistry 2014年04月01日 [査読無し][通常論文]
  • Minoru Waki, Yoshifumi Maegawa, Kenji Hara, Yasutomo Goto, Soichi Shirai, Yuri Yamada, Norihiro Mizoshita, Takao Tani, Wang-Jae Chun, Satoshi Muratsugu, Mizuki Tada, Atsushi Fukuoka, Shinji Inagaki
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 136 10 4003 - 4011 2014年03月 [査読有り][通常論文]
     
    Synthesis of a solid chelating ligand for the formation of efficient heterogeneous catalysts is highly desired in the fields of organic transformation and solar energy conversion. Here, we report the surfactant-directed self-assembly of a novel periodic mesoporous organosilica (PMO) containing 2,2'-bipyridine (bpy) ligands within the framework (BPy-PMO) from a newly synthesized organosilane precursor [(i-PrO)(3)Si-C10H6N2-Si(Oi-Pr)(3)] without addition of any other silane precursors. BPy-PMO had a unique pore-wall structure in which bipyridine groups were densely and regularly packed and exposed on the surface. The high coordination ability to metals was also preserved. Various bipyridine-based metal complexes were prepared using BPy-PMO as a solid chelating ligand such as Ru(bpy)(2)(BPy-PMO), Ir(ppy)(2)(BPy-PMO) (ppy = 2-phenylpyridine), Ir(cod)(OMe)(BPy-PMO) (cod = 1,5-cyclooctadiene), Re(CO)(3)Cl(BPy-PMO), and Pd(OAc)(2)(BPy-PMO). BPy-PMO showed excellent ligand properties for heterogeneous Ir catalyzed direct C H borylation of arenes, resulting in superior activity, durability, and recyclability to the homogeneous analogous Ir catalyst. An efficient photocatalytic hydrogen evolution system was also constructed by integration of a Ru-complex as a photosensitizer and platinum as a catalyst on the pore surface of BPy-PMO without any electron relay molecules. These results demonstrate the great potential of BPy-PMO as a solid chelating ligand and a useful integration platform for construction of efficient molecular-based heterogeneous catalysis systems.
  • Hirokazu Kobayashi, Yuto Hosaka, Kenji Hara, Bo Feng, Yoshihiko Hirosaki, Atsushi Fukuoka
    GREEN CHEMISTRY 16 2 637 - 644 2014年02月 [査読有り][通常論文]
     
    Efficient conversion of cellulose to sorbitol and mannitol by base metal catalysts is a challenge in green and sustainable chemistry, but typical supported base metal catalysts have not given good yields of hexitols or possessed durability. In this study, it has been demonstrated that a simple carbon-supported Ni catalyst affords up to 67% yield of hexitols in the conversion of cellulose, and that the catalyst is durable in the reuse experiments 7 times. In addition, the catalyst can be separated by a magnet thanks to a high content of Ni. Physicochemical analysis has indicated that the use of carbon supports has two benefits: no basicity and high water-tolerance. CeO2, ZrO2, gamma-Al2O3 and TiO2 cause side-reactions due to basicity, and SiO2, gamma-Al2O3 and CeO2 are less stable in hot water. Another important factor is high Ni loading as the increase of Ni content from 10 wt% to 70 wt% significantly improves the yield of hexitols and the durability of catalysts. Larger crystalline Ni particles are more resistant to sintering of Ni and surface coverage by Ni oxide species.
  • Mizuho Yabushita, Hirokazu Kobayashi, Atsushi Fukuoka
    APPLIED CATALYSIS B-ENVIRONMENTAL 145 1 - 9 2014年02月 [査読有り][通常論文]
     
    Conversion of biomass to renewable and valuable chemicals has attracted global interest in order to build up sustainable societies. Cellulose is the most abundant and non-food biomass; however, the low reactivity of cellulose has prevented its use in chemical industry except for the paper manufacturing. The heterogeneous catalysis for the conversion of cellulose has been expected to overcome this issue, because various types of heterogeneous catalysts can be designed and applied in a wide range of reaction conditions. Furthermore, solid catalysts are easily recovered and reused. In this review article, we show the present situation and perspective of heterogeneous catalysis for the transformation of cellulose into useful platform chemicals. (C) 2013 Elsevier B.V. All rights reserved.
  • 菅野周一, 川崎透, 松原宏文, 原賢二, 福岡淳
    化学工学論文集 40 2 104 - 111 The Society of Chemical Engineers, Japan 2014年 [査読有り][通常論文]
     
    酸素および高濃度水蒸気共存下でのPt/Al2O3触媒による水素酸化反応において,反応ガス中に揮発性低分子シロキサン(デカメチルシクロペンタシロキサン(D5))が存在すると,触媒表面にD5が吸着して水素酸化率が低下した.高い触媒活性を維持するため,反応ガスを各種金属酸化物(除去材),触媒の順で接触させ,触媒を通過した後のガス中の水素濃度経時変化を調べた.その結果,各種除去材がD5を反応ガス中から除去し,触媒の水素酸化率低下を抑制することがわかった.特に,ZrO2, メソ多孔体であるSBA-15やMCM-41は高いD5除去性能を示し,Si–O骨格にZr, Tiを組み込んだZr-SBA-15, Ti-SBA-15は新規な酸点が発現し,SBA-15の除去性能を向上した.Zr-SBA-15をコートしたハニカムのみを用いたD5除去試験において,ハニカムを通過したガス中に未分解のD5とCH4が検出された.ハニカムに流通させたD5と,未分解のD5とCH4でハニカム前後の炭素収支がほぼ100%となり,D5は加水分解して除去されていることを確認した.アレニウスプロットから加水分解反応の次数はD5濃度に対し一次であった.
  • 吉井 泰雄, 菅野 周一, 松原 宏文, 川嵜 透, 原 賢二, 福岡 淳
    KAGAKU KOGAKU RONBUNSHU 40 5 420 - 424 The Society of Chemical Engineers, Japan 2014年 [査読有り][通常論文]
     
    沸騰水型原子力発電システム用の再結合触媒を環状シロキサン(D類)被毒から保護するために,再結合触媒の上流に設置する規則メソ多孔体(Zr-SBA15およびTi-SBA15)を担持したハニカム触媒のD5加水分解性能におよぼす諸因子の影響を評価した.D5加水分解反応の除去率は,滞留時間に大きく依存し,反応温度,触媒担持量(50–150 g/L)の影響はほとんどなかった.線速度2.9 m/s,ハニカム高さ120 mmでは423–523 Kの温度領域でD5除去率は0.95という高い値を示した.本反応系でのD5除去率は1次反応式と頻度因子を線速度の関数としたアレニウスプロットから予測可能である.DSS連続試験での性能低下はTi-SBA15はZr-SBA15に比べて低く,耐久性の点からはTi-SBA15が有望である.
  • Mizuho Yabushita, Hirokazu Kobayashi, Kenji Hara, Atsushi Fukuoka
    CATALYSIS SCIENCE & TECHNOLOGY 4 8 2312 - 2317 2014年 [査読有り][通常論文]
     
    The synthesis of glucose from cellulose is a critical roadblock for establishing a new sustainable cycle of biorefinery to produce bio-based and environmentally-benign chemicals. We have previously demonstrated that the pre-treatment ball-milling of solid cellulose and a solid catalyst ( mix-milling) drastically improves the yield of glucose and oligosaccharides; however, the effect of this type of ball-milling has not been quantitatively evaluated. In this study, we performed several model reactions and found that the mix-milling method drastically enhanced the solid-solid reactions, such as the hydrolysis of insoluble cellulose to soluble oligomers on the solid catalyst, but not liquid-solid reactions. The kinetic study indicated that the rate constant of hydrolysis of cellulose to oligomers using mix-milling was 13-fold higher than that using individual milling. Owing to the fast depolymerisation of cellulose, we achieved a 72% yield of glucose with 97% conversion of cellulose and 74% selectivity at 418 K.
  • Tasuku Komanoya, Hirokazu Kobayashi, Kenji Hara, Wang-Jae Chun, Atsushi Fukuoka
    CHEMCATCHEM 6 1 230 - 236 2014年01月 [査読有り][通常論文]
     
    Efficient hydrolytic hydrogenation of cellulose to sugar alcohols under low H-2 pressures has remained a challenge. This article deals with the conversion of cellulose by using a carbon-supported Ru catalyst under H-2 pressures as low as 0.7-0.9MPa (absolute pressure at room temperature). Kinetic studies revealed that the Ru catalyst not only enhances the hydrolysis of cellulose to glucose and hydrogenation of glucose to sugar alcohols (sorbitol and mannitol), but also the degradation of sugar alcohols to C-2-C-6 polyols and gasses. The degradation path limits the total yield of sugar alcohols to less than 40%. The yield of sugar alcohols is theoretically improved by increasing the ratio of the reaction rates of the cellulose hydrolysis, which is the rate-determining step in the reaction, to the decomposition. Thus, a mix-milling pretreatment of cellulose and the Ru catalyst together selectively accelerated the hydrolysis step and raised the yield up to 68%, whereas the addition of acids in the cellulose conversion was less effective as a result of promotion of side-reactions. These results demonstrate superior applicability of the mix-milling treatment in the depolymerization of cellulose to its monomers.
  • S. Jagtap, Y. Kaji, A. Fukuoka, K. Hara
    Chemical Communications 50 39 5046 - 5048 2014年 [査読有り][通常論文]
     
    A high density monolayer of diisocyanide on gold surface was utilized as a platform of supported Rh catalyst for selective 1,4-hydrogenation of α,β-unsaturated carbonyl compounds. The catalyst exhibited high turnover numbers in a range of 50-000 to 150-000 per Rh atom and showed steady catalyst performance over six recycle usages. © 2014 The Partner Organisations.
  • 山越幸康, 北口敏弘, 上出光志, 小林広和, 福岡淳
    北海道立総合研究機構工業試験場報告 312 25 - 29 2013年09月 [査読無し][通常論文]
  • 福岡淳, 小林広和, 藪下瑞帆
    クリーンエネルギー 22 8 45 - 48 2013年08月10日 [査読無し][通常論文]
  • Hirokazu Kobayashi, Mizuho Yabushita, Tasuku Komanoya, Kenji Hara, Ichiro Fujita, Atsushi Fukuoka
    ACS CATALYSIS 3 4 581 - 587 2013年04月 [査読有り][通常論文]
     
    High-yielding one-pot synthesis of glucose from cellulose and pentoses/hexoses from real biomass is achieved by using simple activated carbons and 0.012% HCl in water. Ball-milling cellulose and the carbon together created good physical contact between the solid substrate and solid catalyst before the reaction, selectively and drastically improving the depolymerization rate of cellulose to oligomers. Thus, our methodology overcomes a major obstacle in this type of reaction, namely, that the collision between a solid catalyst and a solid substrate is limited. Mechanistic studies have suggested that the active sites of the carbons are weakly acidic functional groups, in which cicinal carboxylic and phenolic groups synergistically work for the hydrolysis reaction.
  • Tasuku Komanoya, Hirokazu Kobayashi, Kenji Hara, Wang-Jae Chun, Atsushi Fukuoka
    JOURNAL OF ENERGY CHEMISTRY 22 2 290 - 295 2013年03月 [査読有り][招待有り]
     
    A carbon-supported Ru catalyst, Ru/BP2000, is able to simultaneously convert cellobiose into sorbitol and gluconic acid. This reaction occurs as the result of hydrolytic disproportionation in water at 393 K under an Ar atmosphere, without bases or sacrificial reagents. In-situ XANES measurements suggest that the active Ru species involved is composed of partially oxidized Ru metal.
  • Chuanxia Jiang, Kenji Hara, Atsushi Fukuoka
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 52 24 6265 - 6268 2013年 [査読有り][通常論文]
  • 触媒によるバイオマスから有用化合物への転換反応
    藪下瑞帆, 小林広和, 福岡淳
    表面 2013年 [査読無し][招待有り]
     
    広信社倒産のため、未公開
  • Hirokazu Kobayashi, Atsushi Fukuoka
    GREEN CHEMISTRY 15 7 1740 - 1763 2013年 [査読有り][通常論文]
     
    Lignocellulose is the most abundant non-food biomass and is used as a feedstock for the production of chemicals. Lignocellulose consists of cellulose, hemicellulose and lignin, in which the sugar polymers account for a large portion of the biomass. Sugar compounds obtained from non-food biomass can be the first platform chemicals in the biorefinery. From this viewpoint, this review article mainly deals with the catalytic synthesis and utilisation of sugar derivatives produced from cellulose and hemicellulose using various methodologies from fundamental science to practical use.
  • Hirokazu Kobayashi, Atsushi Fukuoka
    New and Future Developments in Catalysis: Catalytic Biomass Conversion 29 - 52 2013年 [査読有り][通常論文]
  • 小林 広和, 太田 英俊, 福岡 淳
    觸媒 = Catalyst 54 7 444 - 448 触媒学会 2012年12月10日 [査読無し][通常論文]
  • Shuhei Ogo, Ayumu Onda, Yukina Iwasa, Kenji Hara, Atsushi Fukuoka, Kazumichi Yanagisawa
    JOURNAL OF CATALYSIS 296 24 - 30 2012年12月 [査読有り][通常論文]
     
    Strontium phosphate hydroxyapatites (Sr-HAP) with various Sr/P molar ratios were synthesized under hydrothermal conditions. X-ray photoelectron spectroscopy revealed a close correlation between the near-surface and bulk Sr/P molar ratios of catalyst samples. Sr-HAP catalysts show high 1-butanol selectivity in the gas-phase conversion of ethanol. Sr-HAP catalysts with higher Sr/P molar ratios showed higher catalytic activity and 1-butanol selectivity. The density of both relatively strong basic sites and acidic sites was seen to increase with increasing Sr/P molar ratios, though the basic site density was significantly higher than the acidic site density. The rate-determining step in ethanol conversion over Sr-HAP catalysts was considered to be the dimerization process, as aldol condensation is mainly accelerated by base catalysis, which would explain why the Sr-HAP catalysts with higher basic site density showed higher catalytic activity and 1-butanol selectivity. (C) 2012 Elsevier Inc. All rights reserved.
  • Shengjun Huang, Kenji Hara, Atsushi Fukuoka
    CHEMISTRY-A EUROPEAN JOURNAL 18 15 4738 - 4747 2012年04月 [査読有り][通常論文]
     
    We have studied the intrinsic catalytic role of MCM-41 mesoporous silica in preferential oxidation of CO in excess H2 (PROX). Two types of MCM-41 supports (MCM-41A and MCM-41B) were obtained from the same pristine as-synthesized materials by using different procedures for surfactant removal: one-step calcination or two-step extractioncalcination. Although two kinds of Pt catalysts prepared from the MCM-41 supports exhibit high similarity in apparent physicochemical parameters such as Pt morphology, particle-size distribution, electronic states, support architecture, and pore-size distribution, they show a dramatic difference in catalytic activity (ca. 100?% versus 10?% CO conversions at 298 K). This feature motivated us to investigate the catalytic role of MCM-41 in the PROX reaction. By means of infrared experiments with the isotope tracer technique, it was revealed that the reactive microenvironment at the interface between Pt and the MCM-41A support is the origin of the high activity. On the highly active Pt/MCM-41A catalyst, interfacial silanols play a decisive role in the ignition of CO oxidation, and gaseous O2 and H2 are dissociated on CO-free Pt sites created by the interfacial reaction. The dissociated oxygen and hydrogen are proposed to sustain the catalytic cycle in the form of regenerated silanols on the support, which is catalyzed by the Pt surface in the presence of H2.
  • Kenji Hara, Saiko Akahane, Jerzy W. Wiench, Breina R. Burgin, Nobuhiro Ishito, Victor S-Y Lin, Atsushi Fukuoka, Marek Pruski
    JOURNAL OF PHYSICAL CHEMISTRY C 116 12 7083 - 7090 2012年03月 [査読有り][通常論文]
     
    Surface silanol groups in mesoporous silica MCM-41 particles were successfully silylated with trimethylsilyl trifluoromethanesulfonate (TMSOTf). Characterization of modified mesoporous silica materials was conducted using Xray diffraction, infrared spectroscopy, nitrogen absorption, elemental analysis, and solid-state NMR spectroscopy. In particular, extensive use of H-1, C-13, and Si-29 solid-state NMR provided unique insights into the silylation process and served as a key guiding tool for the synthetic effort. Treatment of as-synthesized MCM-41 with TMSOTf was found to selectively and efficiently passivate the external surface of particles without assistance of a base, whereas modification by other silylating reagents, including trimethylchlorosilane (TMCS), N,O-bis(trimethylsilyl)acetamide (BSA), and triethoxymethylsilane (MeSi(OEt)(3)), yielded lower coverage and/or resulted in partial silylation of the internal surface. The Si-29 and H-1 solid-state NMR spectra gave accurate concentrations of silicon sites and densities of trimethylsilyl (TMS) groups on the external and internal surfaces of MCM-41. The H-1 and C-13 NMR spectra revealed the definite structures and concentrations of all organic species present in the silylated samples. These data highlighted the importance of choosing a proper concentration of the silylating reagent and finding the washing and extraction conditions that result in efficient sequestration of the structure directing agent (surfactant) without detachment of grafted species or production of unwanted surface alkoxy groups.
  • John Masani Nduko, Wakako Suzuki, Ken'ichiro Matsumoto, Hirokazu Kobayashi, Toshihiko Ooi, Atsushi Fukuoka, Seiichi Taguchi
    JOURNAL OF BIOSCIENCE AND BIOENGINEERING 113 1 70 - 72 2012年01月 [査読有り][通常論文]
     
    Poly[3-hydroxybutyrate-co-3-hydroxyvalerate(3HV)] was produced in recombinant Escherichia coli LS5218 from ruthenium-catalyzed cellulose hydrolysate and propionate. The strain was found to be resistant to 5-hydroxymethylfurfural (5-HMF), which is a major inhibitory byproduct generated in the cellulose hydrolysis reaction. The 3HV fraction was successfully regulated in the range of 5.6-40 mol%. (C) 2011, The Society for Biotechnology, Japan. All rights reserved.
  • Pengfei Yang, Hirokazu Kobayashi, Kenji Hara, Atsushi Fukuoka
    CHEMSUSCHEM 5 5 920 - 926 2012年 [査読有り][招待有り]
     
    Nickel phosphide catalysts supported on activated carbon were tested for the conversion of cellulose in water. High sorbitol yields of over 60?% were obtained with high cellulose conversions at 503 K and 5 MPa of H2. It is interesting that an amorphous nickel phosphide phase is generated from a crystalline phase during the increase in temperature and that the amorphous phase is responsible for the high yield of sorbitol. The optimization of the reaction parameters indicates that the increase of the amorphous part in the cellulose is the key to obtaining high yields of sorbitol. A phase change of the nickel phosphide is observed, which can be correlated to the change in catalytic activity.
  • Yoshiro Masuyama, Yutaka Sugioka, Shiori Chonan, Noriyuki Suzuki, Masahiro Fujita, Kenji Hara, Atsushi Fukuoka
    JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL 352 81 - 85 2012年01月 [査読有り][通常論文]
     
    Palladium(II)-exchanged hydroxyapatite (PdHAP; Pd/Ca ratio = ca. 1/200) was prepared by ion-exchanging with Ca2+ from calcined hydroxyapatite (2.0 mmol) and Pd(NO3)(2) (0.10 mmol) in water (150 mL) at 70 degrees C for 24h. The PdHAP (1 mol% Pd to aryl bromides) functioned as a catalyst for the Suzuki-Miyaura-type cross-coupling reaction of aryl bromides and potassium aryltrifluoroborates with triphenylphosphine (1 mol%) and excess potassium carbonate at 50 degrees C in methanol under air. This cross-coupling reaction was found to proceed in water, while the rate was slow compared with that in methanol. The heterogeneous PdHAP catalyst was used ten times repeatedly at 50 degrees C in methanol under air, though its catalytic activity gradually declined. XRD and XRF analyses and TEM images revealed that most of palladium species would still be supported as isolated ions on the repeatedly used PdHAP, in spite of the changes of the structure and composition of PdHAP surface at the late stages in the repetitive uses and the partial leaching of Pd species at the initial stages in the repetitive uses. The gradual decline of the catalytic activity might be dependent on either the changes of PdHAP surface at the late stages or the partial leaching of Pd species at the initial stages. Still, heterogeneous PdHAP served as a reusable catalyst for Suzuki-Miyaura-type cross-coupling reaction with potassium aryltrifluoroborates. (C) 2011 Elsevier B.V. All rights reserved.
  • Hirokazu Kobayashi, Hidetoshi Ohta, Atsushi Fukuoka
    CATALYSIS SCIENCE & TECHNOLOGY 2 5 869 - 883 2012年 [査読有り][招待有り]
     
    Conversion of lignocellulose into renewable chemicals and fuels has received great attention for building up sustainable societies. However, the utilisation of lignocellulose in the chemical industry has largely been limited to paper manufacturing because of the complicated chemical structure and persistent property of lignocellulose. Heterogeneous catalysis has the potential to selectively convert lignocellulosic biomass into various useful chemicals, and this methodology has rapidly progressed in the last several years. In this perspective article, we outline our recent approaches on the heterogeneous catalysis for this challenging subject with related literatures.
  • Hirokazu Kobayashi, Tasuku Komanoya, Samar K. Guha, Kenji Hara, Atsushi Fukuoka
    APPLIED CATALYSIS A-GENERAL 409 13 - 20 2011年12月 [査読有り][通常論文]
     
    Conversion of biomass to renewable chemicals and fuels has received significant attention as a means to the sustainable society. The most abundant biomass is cellulose, which is produced from carbon dioxide and water using sunlight: however, the efficient chemical transformation of cellulose has remained a challenge because of its persistent property. Among heterogeneous catalysts, supported metal catalysts have been pointed out as an attractive choice to promote the transformation of cellulose due to their tunable activity and durability. In fact, they have been used for the conversion of cellulose to monomeric sugar derivatives based on various strategies. This article provides an overview of the conversion of cellulose by supported metal catalysts into platform chemicals in the biorefinery. (C) 2011 Elsevier B.V. All rights reserved.
  • Yoshiro Masuyama, Kazuki Yoshikawa, Noriyuki Suzuki, Kenji Hara, Atsushi Fukuoka
    TETRAHEDRON LETTERS 52 51 6916 - 6918 2011年12月 [査読有り][通常論文]
     
    Copper(II)-exchanged hydroxyapatite, prepared by ion-exchanging of Ca(II) in calcium hydroxyapatite [Ca-10(PO4)(6)(OH)(2)] with Cu(NO3)(2) at 70 degrees C in water, functions as a reusable heterogeneous catalyst with neither reducing agents nor bases for azide-alkyne [3+2] cycloaddition at 50 degrees C in water under air. (C) 2011 Elsevier Ltd. All rights reserved.
  • Tasuku Komanoya, Hirokazu Kobayashi, Kenji Hara, Wang-Jae Chun, Atsushi Fukuoka
    APPLIED CATALYSIS A-GENERAL 407 1-2 188 - 194 2011年11月 [査読有り][通常論文]
     
    Ru catalyst supported on mesoporous carbon CMK-3 shows high activity and durability for the hydrolysis of cellulose to glucose in hot compressed water at 503 K. The Ru/CMK-3 catalyst also hydrolyzes cellobiose to glucose in water at 393 K. Several physicochemical methods such as XRD, TEM, XPS, H-2-TPR, O-2-titration, and XAFS were used to characterize active Ru species on CMK-3 and to clarify the formation pathway of the active species. From these studies, we conclude that hydrous Ru oxide RuO2 center dot 2H(2)O is formed on CMK-3 after H-2-reduction of RuCl3/CMK-3 at 673 K and subsequent passivation at room temperature, and that the Ru oxide nanoparticles with a mean diameter of 1.1 nm are highly dispersed on CMK-3. (C) 2011 Elsevier B.V. All rights
  • Meng-Liang Lin, Kenji Hara, Yasuhiro Okubo, Masaaki Yanagi, Hironobu Nambu, Atsushi Fukuoka
    CATALYSIS COMMUNICATIONS 12 13 1228 - 1230 2011年07月 [査読有り][通常論文]
     
    The olefin epoxidation is one of the most important reactions in chemical industry. Metal oxide supports often cause drawbacks in catalytic activity and selectivity, which has been overcome by introducing hydrophobic organic groups onto the oxide supports. The present study utilizes ordered mesoporous carbon (CMK-3 and CMK-1) as structurally defined hydrophobic catalyst support. Well-dispersed tantalum oxides supported on the ordered mesoporous carbon were prepared. Their application in catalytic epoxidation of cyclooctene demonstrates that the tantalum oxide catalysts on the ordered mesoporous carbon supports show higher performances than those of the catalysts supported on activated carbon and ordered mesoporous silica SBA-15. (C) 2011 Elsevier B.V. All rights reserved.
  • 小林 広和, 福岡 淳
    日本エネルギー学会誌 90 6 512 - 517 一般社団法人日本エネルギー学会 2011年06月20日 [査読無し][通常論文]
     
    Conversion of biomass to renewable chemicals and fuels has been paid great attention as one of the future key technologies for the sustainable society. The most abundant biomass is cellulose, produced via photosynthesis using sunlight. However, the utilization of cellulose in the chemical industry has almost been limited to the paper manufacturing because of the persistent property. For this reason, solid catalysts have been applied to the selective conversion of cellulose to sugar alcohols as well as glucose, and this research field has rapidly progressed in recent years. In this review, w...
  • Samar K. Guha, Hirokazu Kobayashi, Kenji Hara, Hiroto Kikuchi, Tsutomu Aritsuka, Atsushi Fukuoka
    CATALYSIS COMMUNICATIONS 12 11 980 - 983 2011年06月 [査読有り][通常論文]
     
    Sugar beet fiber is an agricultural by-product in the sugar manufacturing and an available biomass source with a rich hemicellulose component. So far, there has been no report on the catalytic conversion of the beet fiber for the synthesis of chemicals. In this work, the hydrogenolysis of the beet fiber was studied by using supported metal catalysts under pressurized hydrogen conditions. Activated carbon supported Ru was found to show the highest catalytic activity to give arabitol as a major product in the hydrogenolysis of hemicellulose part of this material. The reuse ability of the catalyst was also investigated. (C) 2011 Elsevier B.V. All rights reserved.
  • Pengfei Yang, Hirokazu Kobayashi, Atsushi Fukuoka
    CHINESE JOURNAL OF CATALYSIS 32 5 716 - 722 2011年05月 [査読有り][通常論文]
     
    Currently, under huge pressure from energy demands and environmental problems, much attention is being paid to biomass conversion, which will play an important role in meeting the requirements for a sustainable society. As the most abundant biomass on earth, cellulose is usually used as the first research target for biomass conversion. In this review, the recalcitrant structure of cellulose is discussed and non-catalytic hydrolysis by hot-compressed water and catalytic hydrolysis using solid acids are then considered. We also review the catalytic conversion of cellulose into valuable chemicals including hexitols (sorbitol and mannitol), ethylene glycol, and related compounds using various heterogeneous catalysts.
  • Pengfei Yang, Hirokazu Kobayashi, Atsushi Fukuoka
    CHINESE JOURNAL OF CATALYSIS 32 5 716 - 722 2011年05月 [査読有り][通常論文]
     
    Currently, under huge pressure from energy demands and environmental problems, much attention is being paid to biomass conversion, which will play an important role in meeting the requirements for a sustainable society. As the most abundant biomass on earth, cellulose is usually used as the first research target for biomass conversion. In this review, the recalcitrant structure of cellulose is discussed and non-catalytic hydrolysis by hot-compressed water and catalytic hydrolysis using solid acids are then considered. We also review the catalytic conversion of cellulose into valuable chemicals including hexitols (sorbitol and mannitol), ethylene glycol, and related compounds using various heterogeneous catalysts.
  • Ken'ichiro Matsumoto, Hirokazu Kobayashi, Koji Ikeda, Tasuku Komanoya, Atsushi Fukuoka, Seiichi Taguchi
    BIORESOURCE TECHNOLOGY 102 3 3564 - 3567 2011年02月 [査読有り][通常論文]
     
    Cellulose-derived glucose generated using the supported ruthenium catalyst was applied to poly(3-hydroxybutyrate) [P(3HB)] production in recombinant Escherichia coli. By the reaction with the catalyst at 220 degrees C. 15-20 carbon mol% of cellulose was converted into glucose. The hydrolysate also contained byproducts such as fructose, mannose, levoglucosan, oligomeric cellulose, 5-hydroxymethylfurfural (5-HMF), and furfural together with unidentified compounds. Setting the reaction temperature lower (215 degrees C) improved the ratio of glucose to 5-HMF, which was a main inhibiting factor for the cell growth. Indeed, the recombinant E. coli exhibited better performance on the hydrolysate generated at 215 degrees C and accumulated P(3HB) up to 42 wt%, which was the same as the case of the same concentration of analytical grade glucose. The result indicated that the ruthenium-mediated cellulose hydrolysis has a potency as a useful biorefinery process for production of bio-based plastic from cellulosic biomass. (C) 2010 Elsevier Ltd. All rights reserved.
  • Hirokazu Kobayashi, Hisateru Matsuhashi, Tasuku Komanoya, Kenji Hara, Atsushi Fukuoka
    CHEMICAL COMMUNICATIONS 47 8 2366 - 2368 2011年 [査読有り][通常論文]
     
    Ru/C catalysts are active for the conversion of cellulose using 2-propanol or H-2 of 0.8 MPa as sources of hydrogen, whereas the Ru/Al2O3 catalyst is inactive in both reactions, indicating that the Ru/C catalysts are remarkably effective for the cellulose conversion.
  • Hidetoshi Ohta, Hirokazu Kobayashi, Kenji Hara, Atsushi Fukuoka
    CHEMICAL COMMUNICATIONS 47 44 12209 - 12211 2011年 [査読有り][通常論文]
     
    Carbon-supported Pt catalysts are highly active and reusable for the aqueous-phase hydrodeoxygenation of phenols as lignin models without adding any acids. It is suggested that Pt/carbon facilitates the hydrogenation of phenols and the hydrogenolysis of the resulting cyclohexanols.
  • Hirokazu Kobayashi, Yukiko Ito, Tasuku Komanoya, Yuto Hosaka, Paresh L. Dhepe, Koji Kasai, Kenji Hara, Atsushi Fukuoka
    GREEN CHEMISTRY 13 2 326 - 333 2011年 [査読有り][通常論文]
     
    Cellulose is converted into sorbitol and related sugar compounds over water-tolerant and durable carbon-supported Pt catalysts under aqueous hydrogenation conditions. Pre-treatment of cellulose with ball-milling effectively reduces the crystallinity and particle size of cellulose, which results in high conversion of cellulose to sorbitol and mannitol. The selectivity of sorbitol increases by using Cl-free metal precursors in the catalyst preparation as residual Cl on the catalysts promotes the side-reactions. The transformation of cellulose to sorbitol consists of the hydrolysis of cellulose to glucose via water-soluble oligosaccharides and the successive hydrogenation of glucose to sorbitol. The hydrolysis of cellulose is the rate-determining step, and the Pt catalysts promote both the hydrolysis and the hydrogenation steps.
  • 小林 広和, 福岡 淳
    ペトロテック = Petrotech 34 1 18 - 23 石油学会 2011年01月01日 [査読無し][通常論文]
  • 小林 広和, 福岡 淳
    ファインケミカル 39 6 13 - 19 シーエムシー出版 2010年06月 [査読無し][通常論文]
  • Hirokazu Kobayashi, Tasuku Komanoya, Kenji Hara, Atsushi Fukuoka
    CHEMSUSCHEM 3 4 440 - 443 2010年 [査読有り][通常論文]
  • 小林 広和, 福岡 淳
    未来材料 10 1 39 - 43 エヌ・ティー・エス 2010年01月 [査読無し][通常論文]
  • Guha S.K, Kobayashi H, Fukuoka A
    RSC Energy and Environment Series 2010 1 344 - 364 2010年 [査読有り][通常論文]
  • Shengjun Huang, Kenji Hara, Yasuhiro Okubo, Masaaki Yanagi, Hironobu Nambu, Atsushi Fukuoka
    APPLIED CATALYSIS A-GENERAL 365 2 268 - 273 2009年08月 [査読有り][通常論文]
     
    Preferential oxidation (PROX) of carbon monoxide in excess hydrogen has been studied on low Pt loading (0.5-1 wt%) catalysts supported on a series of FSM-type mesoporous silica materials. A support effect has been observed, in which the catalytic activities are closely related with the pore diameter of the support, despite their similar specific surface areas. Pt nanoparticles supported on mesoporous silica with 4.0 nm pore diameter possess the highest CO conversion over a wide range of reaction temperature, i.e. ca. 100% CO conversion in 298-423 K. As a comparison, the Pt particles in small pore supports (1.8 nm) exhibit poor performance under the same reaction conditions, which is barely comparable to the Pt catalysts on amorphous silica. The discrepancy in the mesoporous silica is proposed to be related with the different activities of surface silanols in various supports. (C) 2009 Elsevier B.V. All rights reserved.
  • Soichiro Kawamorita, Hirohisa Ohmiya, Kenji Hara, Atsushi Fukuoka, Masaya Sawamura
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 131 14 5058 - + 2009年04月 [査読有り][通常論文]
     
    An immobilized monophosphine-Ir system, which was prepared in situ from [Ir(OMe)(cod)](2) and a silica-supported, compact phosphine, showed high activities and selectivities for the borylation of aromatic C-H bonds with bis(pinacolato)diboron. This system was effective not only for the borylation of benzene but also for the ortho borylation of arenes with directing groups, such as ester, amide, sulfonate, acetal, alkoxymethyl, and chloro groups, under mild reaction conditions.
  • Atsushi Fukuoka, Paresh L. Dhepe
    CHEMICAL RECORD 9 4 224 - 235 2009年 [査読有り][通常論文]
     
    The recent progress of sustainable green catalysis by supported metal nanoparticles is described. The template synthesis of metal nanoparticles in ordered porous materials is studied for the rational design of heterogeneous catalysts capable of high activity and selectivity. The application of these materials in green catalytic processes results in a unique activity and selectivity arising from the concerted effect of metal nanoparticles and supports. The high catalytic performances of Pt nanoparticles in mesoporous silica is reported Supported metal catalysts have also been applied to biomass conversion by heterogeneous catalysis Additionally, the degradation of cellulose by supported metal catalysts, in which bifunctional catalysis of acid and metal plays the key role for the hydrolysis and reduction of cellulose, is also reported. (C) 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 9: 224-235: 2009: Published online in Wiley InterScience (www.intersciencewiley.corn) DOI 10.1002/tcr.200900004
  • Tatsuo Kimura, Shengjun Huang, Atsushi Fukuoka, Kazuyuki Kuroda
    JOURNAL OF MATERIALS CHEMISTRY 19 23 3859 - 3866 2009年 [査読有り][通常論文]
     
    Properties arising from 2-D orthorhombic mesoporous silica (KSW-2) were investigated for each structural feature: (1) periodicity in silicate framework and (2) square-shape mesopore. Titanium species were grafted onto the periodic silica walls of KSW-2-based mesoporous silica through silylation with octylmethyldichlorosilane in the presence of organotitanium compounds with cyclopentadienyl ligands. The surface TiO(4) units formed after calcination at 550 degrees C showed a higher activity in the oxidation of cyclohexene with peroxides than those onto FSM-16 and MCM-41 grafted in the same manner, indicating that (1) the periodicity in the framework influenced the catalytic activity due to the heteroatoms fixed at the silicate surfaces. The synthesis of metallic Pt species inside square-shape mesopores of KSW-2-based silica was conducted by reduction of impregnated H(2)PtCl(6). Considering the morphology of metallic Pt species formed through wet H(2) and UV reduction, it is considered that (2) the square-shape mesopore is useful for suppressing the sintering of metallic Pt species.
  • Shengjun Huang, Kenji Hara, Atsushi Fukuoka
    ENERGY & ENVIRONMENTAL SCIENCE 2 10 1060 - 1068 2009年 [査読有り][通常論文]
     
    Preferential oxidation of carbon monoxide in excess hydrogen (PROX) is one of the key processes for the production of clean hydrogen fuel for the polymer electrolyte membrane fuel cell (PEFC). Development of highly active and selective catalysts is among the most challenging works for decades. Platinum-based catalysts are regarded as the most promising candidates for this process. However, the activities of Pt catalysts seriously suffer from the strong poisonous adsorption by CO substrate at low reaction temperature. This article addresses the present approaches to improve catalytic performance at low temperature. The focus of this article is a new reaction route of CO oxidation over Pt/mesoporous silica under PROX reaction conditions. The high activity and selectivity of this catalyst has been attributed to the surface silanols in mesoporous silica. The perspectives of Pt/mesoporous silica in the PROX reaction are also presented.
  • Go Hamasaka, Soichiro Kawamorita, Atsuko Ochida, Ryuto Akiyama, Kenji Hara, Atsushi Fukuoka, Kiyotaka Asakura, Wang Jae Chun, Hirohisa Ohmiya, Masaya Sawamura
    ORGANOMETALLICS 27 24 6495 - 6506 2008年12月 [査読有り][通常論文]
     
    Solid-supported phosphine ligands silica-SMAPs {[silica gel 60N]-SMAP (1a) or [CARiACT Q-10]-SMAP (1b)}, which are composed of a caged, compact trialkylphosphine (SMAP) as a ligand and silica gel (silica get 60N or CARiACT Q-10) as a support,'were synthesized through surface functionalization. The supported phosphines (1a,b) were structurally characterized by solid-state (13)C, (29)Si, and (31)P cross-polarization/magic angle spinning (CP/MAS) NMR spectroscopies and N(2) adsorption measurements. Complexation of 1a,b with [RhCl(cod)](2) afforded a mono(phosphine)-rhodium complex Silica-SMAP-RhCl(cod) exclusively, even in the presence of excess ligands, as proved by solid-state (13)C and (31)P CP/MAS NMR spectroscopies and Rh K-edged X-ray'absorption fine structure (XAFS) measurements. Heterogeneous catalysts that were prepared from [RhCl(C(2)H(4))(2)](2) and 1a,b showed exceptionally high catalytic activities for the reaction of sterically hindered ketones (including di-tertbutyl ketone) and triorganosi lanes such as Et(3)SiH and (t-Bu)Me(2)SiH. The catalyst from 1b showed no leaching of rhodium after reaction and was reusable without decrease of the activity.
  • Ken-ichi Tanaka, Masashi Shou, Hongbin Zhang, Youzhu Yuan, Tokio Hagiwara, Atsushi Fukuoka, Junji Nakamura, Daling Lu
    CATALYSIS LETTERS 126 1-2 89 - 95 2008年11月 [査読有り][通常論文]
     
    Pt catalyst supported on carbon nano-tube (CNT) was extremely active for the selective oxidation of CO in H(2) at room temperature, which was remarked contrast to the Pt supported on an active carbon (Vulcan carbon) and a graphite powder. Complete oxidation of CO was attained on a 5 wt.% Pt/CNT catalyst (0.8 g) at ca. 40 degrees C when the O(2)/CO ratio in a flow of H(2) (20 mL/min) + CO (3.0 mL/min) + O(2) + N(2) was adjusted to be larger than 0.75 at the total flow rate of 100 mL/min. Specific activity of the Pt/CNT catalyst was explained by efficient provision of reactant molecules diffusing on CNT surface to Pt particles.
  • Soichiro Kawamorita, Go Hamasaka, Hirohisa Ohmiya, Kenji Hara, Atsushi Fukuoka, Masaya Sawamura
    ORGANIC LETTERS 10 20 4697 - 4700 2008年10月 [査読有り][通常論文]
     
    A heterogeneous mono(phosphine)-Rh catalyst system silica-SMAP-Rh(OMe)(cod), where silica-SMAP stands for a caged, compact trialkylphosphine (SMAP) supported on silica gel, showed broad applicability toward the hydrogenation of hindered ketones. Doubly a-branched ketones such as diisopropyl ketone was hydrogenated under nearly atmospheric conditions. Di-tert-butyl ketone could be hydrogenated under more forcing conditions.
  • Paresh L. Dhepe, Atsushi Fukuoka
    CHEMSUSCHEM 1 12 969 - 975 2008年 [査読有り][通常論文]
     
    In view of current problems such as global warming, high oil prices, food crisis, stricter environmental laws, and other geopolitical scenarios surrounding the use of fossil feedstocks and edible resources, the efficient conversion of cellulose, a non-food biomass, into energy, fuels, and chemicals has received much attention. The application of heterogeneous catalysis could allow researchers to develop environmentally benign processes that lead to selective formation of value-added products from cellulose under relatively mild conditions. This Minireview gives insight into the importance of biomass utilization, the current status of cellulose conversion, and further transformation of the primary products obtained
  • Paresh L. Dhepe, Atsushi Fukuoka
    CATALYSIS SURVEYS FROM ASIA 11 4 186 - 191 2007年12月 [査読有り][通常論文]
     
    Cellulose is cracked over supported Pt or Ru catalysts under hydrogenolysis conditions in water to give sorbitol as a main product. Among the catalysts tested, Pt/gamma-Al2O3 gave the highest yield and selectivity, and this catalyst was recyclable in repeated runs. It is proposed that cellulose is hydrolyzed by in situ generated acid sites to form glucose, and glucose is immediately reduced to sorbitol over the metal catalyst.
  • Atsushi Fukuoka, Jun-ichi Kimura, Tadashi Oshio, Yuzuru Sakamoto, Masaru Ichikawa
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 129 33 10120 - 10125 2007年08月 [査読有り][通常論文]
     
    Preferential oxidation (PROX) of CO is an important practical process to purify H-2 for use in polymer electrolyte fuel cells. Although many supported noble metal catalysts have been reported so far, their catalytic performances remain insufficient for operation at low temperature. We found that Pt nanoparticles in mesoporous silica give unprecedented activity, selectivity, and durability in the PROX reaction below 353 K. We also studied the promotional effect of mesoporous silica in the Pt-catalyzed PROX reaction by infrared spectroscopy using the isotopic tracer technique. Gas-phase O-2 is not directly used for CO oxidation, but the oxygen of mesoporous silica is incorporated into CO2. These results suggest that CO oxidation is promoted by the attack of the surface OH groups to CO on Pt without forming water.
  • 福岡 淳
    未来材料 7 3 28 - 34 エヌ・ティー・エス 2007年03月 [査読無し][通常論文]
  • Yusuke Ide, Atsushi Fukuoka, Makoto Ogawa
    CHEMISTRY OF MATERIALS 19 5 964 - 966 2007年03月 [査読有り][通常論文]
  • 福岡 淳
    Cellulose communications 14 2 67 - 70 セルロ-ス学会 2007年 [査読有り][通常論文]
  • Atsushi Fukuoka, Masaru Ichikawa
    TOPICS IN CATALYSIS 40 1-4 103 - 109 2006年11月 [査読有り][通常論文]
     
    Pt nanowires and nanoparticles were selectively synthesized in mesoporous silica templates FSM-16 and HMM. The wires and particles were characterized by physicochemical methods. Extracted Pt nanoparticles on HOPG show Coulomb blockade phenomena in STM/STS measurements. Pt nanowires and -particles in FSM-16 shows high catalytic activity and selectivity in preferential oxidation (PROX) of CO in H-2.
  • Atsushi Fukuoka, Yuzuru Sakamoto, Takanori Higuchi, Noriyuki Shimomura, Masaru Ichikawa
    JOURNAL OF POROUS MATERIALS 13 3-4 231 - 235 2006年10月 [査読有り][通常論文]
     
    Platinum nanowires and nanoparticles were selectively synthesized in mesoporous silicas FSM-16 and HMM-1. The nanowires are 3 nm in diameter and several hundred nm to mu m in length with high crystallinity. Pt nanowires and nanoparticles can be isolated by dissolving silica matrix with HF. The Pt wires extracted from organosilica HMM-1 have a nanonecklace structure, while the wires from siliceous FSM-16 have a nanorod structure. The extracted Pt nanoparticles (3 nm in size) on HOPG show the Coulomb staircase phenomena in STM/STS analysis. The mechanism for formation of the Pt nanowires is based on the migration of Pt ions in the mesoporous channels.
  • Y Kumai, H Tsukada, Y Akimoto, N Sugimoto, Y Seno, AT Fukuoka, M Ichikawa, S Inagaki
    ADVANCED MATERIALS 18 6 760 - + 2006年03月 [査読有り][通常論文]
     
    Highly ordered Pt nanodot arrays with cubic symmetry are synthesized by simple immersion of mesoporous silica thin films into a Pt precursor solution followed by photoreduction. Two types of cages of mesoporous thin films have been fully filled with Pt nanoparticles approximately 4 nm in size, and an exceptionally well-ordered cubic lattice array of nanodots has been obtained (see figure).
  • N Kariya, A Fukuoka, M Ichikawa
    PHYSICAL CHEMISTRY CHEMICAL PHYSICS 8 14 1724 - 1730 2006年 [査読有り][通常論文]
     
    A series of "organic chemical hydrides'' such as cyclohexane, methylcyclohexane, cyclohexene, 2-propanol, and cyclohexanol were applied to the direct PEM fuel cell. High performances of the PEM fuel cell were achieved by using cyclohexane (OCV = 920 mV, PDmax = 15 mW cm(-2)) and 2-propanol ( OCV = 790 mV, PDmax = 78 mW cm(-2)) as fuels without CO2 emissions. The rates of fuel crossover for cyclohexane, 2-propanol, and methanol were estimated, and the rates of fuel permeation of cyclohexane and 2-propanol were lower than that of methanol. Water electrolysis and electro-reductive hydrogenation of acetone mediated by PEM were carried out and formation of 2-propanol in cathode side was observed. This system is the first example of a "rechargeable'' direct fuel cell.
  • Atsushi Fukuoka, Paresh L. Dhepe
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 45 31 5161 - 5163 2006年 [査読有り][通常論文]
  • A Fukuoka, T Higuchi, T Ohtake, T Oshio, J Kimura, Y Sakamoto, N Shimomura, S Inagaki, M Ichikawa
    CHEMISTRY OF MATERIALS 18 2 337 - 343 2006年01月 [査読有り][通常論文]
     
    Nanowires of platinum and gold with high aspect ratios are synthesized in one-dimensional channels of ordered mesoporous organosilica HMM. Water-saturated hydrogen reduction (wet H-2-reduction) is significantly effective for large-scale synthesis of long nanowires, while dry H-2-reduction gives monodispersed metal nanoparticles. The nanowires are characterized by TEM, XRD, UV-vis, STM, and XAFS. The Pt and Au wires are 3 nm in diameter and several hundred nanometers to micrometers in length. The metal wires extracted from HMM with HF have a nanonecklace structure, while the wires from siliceous FSM-16 have a nanorod structure. The results indicate that the hydrophobicity or hydrophilicity of the internal pore gives a significant influence on the morphology of nanowires. The nanonecklace structure is also affected by the organic groups in HMM. The mechanism for formation of Pt nanowires in wet H-2-reduction was studied. In the impregnation process, the [PtCl6](2-) ion is physically adsorbed on HMM, and the Pt(IV) ion is reduced to Pt(0) via Pt(II). Tiny Pt nanoparticles are formed in the mesoporous channels, and the water vapor in the H-2 flow enhances the migration of Pt ions, leading to the growth of long nanowires.
  • PL Dhepe, M Ohashi, S Inagaki, M Ichikawa, A Fukuoka
    CATALYSIS LETTERS 102 3-4 163 - 169 2005年08月 [査読有り][通常論文]
     
    Mesoporous silicas are modified with sulfonic acid groups either by one-pot or by grafting method. In the hydrolysis of sucrose and starch, the sulfonated mesoporous silicas work as water-tolerant recyclable solid acid catalysts, showing higher conversion and turnover frequency than conventional Amberlyst-15, Nafion-silica and HZSM-5 catalysts.
  • 福岡 淳
    ファインケミカル 34 5 11 - 18 シーエムシー出版 2005年05月 [査読無し][通常論文]
  • MT Bore, HN Pham, EE Switzer, TL Ward, A Fukuoka, AK Datye
    JOURNAL OF PHYSICAL CHEMISTRY B 109 7 2873 - 2880 2005年02月 [査読有り][通常論文]
     
    Highly dispersed gold particles (<2 nm) were synthesized within the pores of mesoporous silica with pore sizes ranging from 2.2 to 6.5 nm and different pore structures (2D-hexagonal, 3D-hexagonal, and cubic). The catalysts were reduced in flowing H-2 at 200 degreesC and then used for CO oxidation at temperatures ranging from 25 to 400 degreesC. The objective of this study was to investigate the role of-pore size and structure in controlling the thermal sintering of An nanoparticles. Our study shows that sintering of An particles is dependent on pore size, pore wall thickness (strength of pores), and pore connectivity. A combination of high-resolution TEM/STEM and SEM was used to measure the particle size distribution and to determine whether the An particles were located within the pores or had migrated to the external silica surface.
  • 仮屋 伸子, Rajesh Biniwale, 福岡 淳, 市川 勝
    日本エネルギー学会大会講演要旨集 14 260 - 261 一般社団法人日本エネルギー学会 2005年
  • Atsusi Fukuoka, Masaru Ichkawa
    INTERNATIONAL JOURNAL OF NANOSCIENCE, VOL 4, NOS 5 AND 6 4 5-6 957 - 963 2005年 [査読有り][通常論文]
     
    Mono- and bimetallic nanowires and particles were selectively synthesized in mesoporous silica templates, in which siliceous FSM-16 and organic-inorganic hybrid HMM-1 were used as templates. The metal nanowires and particles were characterized by several physicochemical methods. The mechanism for formation of Pt wires was studied, and migration of precursor Pt ions in the mesoporous channels is the key to the formation of the wires. The Pt wires can be isolated by dissolving silicate matrix in a good yield, and STM and HRTEM demonstrate that the wires extracted from HMM-13 has a nanonecklace structure, but the wire from FSM-16 shows a nanorod structure. The extracted Pt wires are stabilized by PPh3. The nanowire composites show unique properties in magnetism and high catalytic performances in CO oxidation reaction.
  • MT Bore, TL Ward, A Fukuoka, AK Datye
    CATALYSIS LETTERS 98 4 167 - 172 2004年12月 [査読有り][通常論文]
     
    Spherical mesoporous silica particles prepared by evaporation induced self assembly (EISA) were used as templates to form Pt nanowires. Transmission electron microscope (TEM) images of these aerosol-derived silica particles reveal hexagonally ordered pores coiled within each particle, with no obvious termination of the pores on the external surface. Near the particle surface the pores are seen to run parallel to the surface, consistent with the external constraint of spherical geometry. For MCM-41 type mesoporous materials, the pores are straight and accessible at either end for pore filling, but for spherical silica particles prepared by EISA, the pores are not open to the external surface. Hence it is remarkable that Pt nanowires can be formed within the closed pores inside these spherical silica particles, where conventional mechanisms of pore filling would not be expected to be operative. These results suggest that the silica walls in these mesoporous silica allow transport of volatile Pt complexes during wet reduction in H-2. The permeability to gases makes these spherical silica particles especially suitable for gas phase catalytic reactions, while at the same time confining metallic particles within the silica pores.
  • A Fukuoka, H Araki, J Kimura, Y Sakamoto, T Higuchi, N Sugimoto, S Inagaki, M Ichikawa
    JOURNAL OF MATERIALS CHEMISTRY 14 4 752 - 756 2004年02月 [査読有り][通常論文]
     
    Mesoporous silica films were prepared on glass plates by a dip coating method, and the film/plate samples were used as a support for Au, Pt and Pd nanoparticles. By H-2- or photo-reduction of metal precursors impregnated on the films, metal nanoparticles are formed with an ordered array structure in the mesopores. The nanoparticles are isolated by dissolving the silica film with a dilute HF solution, and the particles are stabilized with ligands such as 1-dodecanethiol and triphenylphosphine. The diameter of the separated nanoparticles is 2.5 nm with narrow distributions, showing that uniform particles are formed in the mesopores. Selective formation of metal nanoparticles rather than nanowires suggests that a 3D-hexagonal structure is involved in the 2D-hexagonal mesoporous silica films. To study the formation of nanoparticles in a 3D-hexagonal structure, HMM-2 powder was used as a support, and in fact Au and Pt nanoparticles are formed in the HMM-2 powders. The XRD study suggests that the Au nanoparticles in the film/plate have an anisotropic orientation in the mesoporous channels. The Au/film/plate sample gives a weak plasmon peak at 570-580 nm using diffuse-reflectance UV-visible spectroscopy, which is shifted to high wavelength by 50-60 nm compared with larger Au particles.
  • A Fukuoka, H Araki, J Kimura, Y Sakamoto, T Higuchi, N Sugimoto, S Inagaki, M Ichikawa
    JOURNAL OF MATERIALS CHEMISTRY 14 4 752 - 756 2004年02月 [査読有り][通常論文]
     
    Mesoporous silica films were prepared on glass plates by a dip coating method, and the film/plate samples were used as a support for Au, Pt and Pd nanoparticles. By H-2- or photo-reduction of metal precursors impregnated on the films, metal nanoparticles are formed with an ordered array structure in the mesopores. The nanoparticles are isolated by dissolving the silica film with a dilute HF solution, and the particles are stabilized with ligands such as 1-dodecanethiol and triphenylphosphine. The diameter of the separated nanoparticles is 2.5 nm with narrow distributions, showing that uniform particles are formed in the mesopores. Selective formation of metal nanoparticles rather than nanowires suggests that a 3D-hexagonal structure is involved in the 2D-hexagonal mesoporous silica films. To study the formation of nanoparticles in a 3D-hexagonal structure, HMM-2 powder was used as a support, and in fact Au and Pt nanoparticles are formed in the HMM-2 powders. The XRD study suggests that the Au nanoparticles in the film/plate have an anisotropic orientation in the mesoporous channels. The Au/film/plate sample gives a weak plasmon peak at 570-580 nm using diffuse-reflectance UV-visible spectroscopy, which is shifted to high wavelength by 50-60 nm compared with larger Au particles.
  • Y Sakamoto, A Fukuoka, T Higuchi, N Shimomura, S Inagaki, M Ichikawa
    JOURNAL OF PHYSICAL CHEMISTRY B 108 3 853 - 858 2004年01月 [査読有り][通常論文]
     
    Pt nanowires are synthesized in organic-inorganic mesoporous silica HMM-1 (channel diameter 3 nm) by photoreduction, and the formation mechanism and isolation of the wires have been studied. UV-irradiation of HMM-1 impregnated with H2PtCl6 for 48 h in the presence of adsorbed water and methanol leads to the formation of Pt nanowires (diameter 3 nm, length up to 5 mum) in the one-dimensional channels. On the other hand, H-2-reduction of H2PtCl6/HMM-1 at 443 K for 2 h results in the formation of Pt nanoparticles (diameter 3 nm) and short wires in the channels. The formation mechanism of the wires has been studied by transmission electron microscopy (TEM), X-ray absorption fine structure (XAFS), and powder X-ray diffraction (XRD), and it is suggested that Pt ions migrate in the water/methanol phase and are catalytically reduced on Pt particles to grow to wires. In the H-2-reduction, however, the reduction of Pt ions is faster than the migration, thus resulting in the formation of nanoparticles. The Pt wires are isolated by removing HMM-1 with HF treatment (yield 66%). The unsupported Pt wires are stabilized by ligands such as [N(C18H37)(CH3)(3)]Cl and P(C6H5)(3). Scanning tunneling microscope (STM) observation of the isolated Pt wires on highly oriented pyrolytic graphite (HOPG) confirms that the wires separated from HMM-1 have a necklace-like structure, while the wires from pure siliceous FSM-16 have a rodlike structure.
  • Y Sakamoto, A Fukuoka, T Higuchi, N Shimomura, S Inagaki, M Ichikawa
    JOURNAL OF PHYSICAL CHEMISTRY B 108 3 853 - 858 2004年01月 [査読有り][通常論文]
     
    Pt nanowires are synthesized in organic-inorganic mesoporous silica HMM-1 (channel diameter 3 nm) by photoreduction, and the formation mechanism and isolation of the wires have been studied. UV-irradiation of HMM-1 impregnated with H2PtCl6 for 48 h in the presence of adsorbed water and methanol leads to the formation of Pt nanowires (diameter 3 nm, length up to 5 mum) in the one-dimensional channels. On the other hand, H-2-reduction of H2PtCl6/HMM-1 at 443 K for 2 h results in the formation of Pt nanoparticles (diameter 3 nm) and short wires in the channels. The formation mechanism of the wires has been studied by transmission electron microscopy (TEM), X-ray absorption fine structure (XAFS), and powder X-ray diffraction (XRD), and it is suggested that Pt ions migrate in the water/methanol phase and are catalytically reduced on Pt particles to grow to wires. In the H-2-reduction, however, the reduction of Pt ions is faster than the migration, thus resulting in the formation of nanoparticles. The Pt wires are isolated by removing HMM-1 with HF treatment (yield 66%). The unsupported Pt wires are stabilized by ligands such as [N(C18H37)(CH3)(3)]Cl and P(C6H5)(3). Scanning tunneling microscope (STM) observation of the isolated Pt wires on highly oriented pyrolytic graphite (HOPG) confirms that the wires separated from HMM-1 have a necklace-like structure, while the wires from pure siliceous FSM-16 have a rodlike structure.
  • PL Dhepe, A Fukuoka, M Ichikawa
    PHYSICAL CHEMISTRY CHEMICAL PHYSICS 5 24 5565 - 5573 2003年12月 [査読有り][通常論文]
     
    Mesoporous HMM-1 and FSM-16 supported monometallic Rh and bimetallic RhPt catalysts have been prepared by applying supercritical carbon dioxide (scCO(2)) treatment (348 K and 16 MPa) to metal precursors impregnated on the supports followed by calcination and H-2-reduction. The catalysts thus prepared were characterized by CO chemisorption, XRD, TEM and IR spectroscopy to elucidate the morphology of the metal particles and support. The characterization data revealed that highly dispersed Rh and RhPt nano-sized particles (particle size <3 nm) were obtained after the scCO(2) treatment inside the mesoporous channels of the supports. Homogeneous alloy particles were obtained for the RhPt catalysts after the treatments. Catalytic performances were tested for butane hydrogenolysis. Marked enhancement in the catalytic activity and selectivity for ethane production due to central C-C bond scission was observed for the scCO(2) treated Rh and RhPt catalysts relative to the non-treated conventional catalysts.
  • A Fukuoka, H Araki, Y Sakamoto, S Inagaki, Y Fukushima, M Ichikawa
    INORGANICA CHIMICA ACTA 350 371 - 378 2003年07月 [査読有り][通常論文]
     
    Nanowires and nanoparticles of palladium are synthesized in mesoporous silicas FSM-16 and HMM-1, and their structural characterization and catalytic performances in CO oxidation have been studied. FSM-16 and HMM-1 were impregnated with H2PdCl4. and the thermal treatment under O-2 or N-2 atmosphere led to high dispersion of H2PdCl4 into the one-dimensional channels of the mesoporous materials (channel diameter ca. 3 nm). UV-irradiation of the sample in the presence of water and methanol vapors and subsequent H-2-reduction resulted in the formation of Pd nanowires with the diameter less than 3 nm and the length up to 300 nm. In contrast, one-step H-2-reduction gave Pd nanoparticles in the mesopores. The Pd nanowires and nanoparticles were characterized by means of TEM, XRD, XAFS, and CO uptake. CO oxidation was performed as a test reaction to compare catalytic performances of the Pd nanowires and nanoparticles. (C) 2003 Elsevier Science B.V. All rights reserved.
  • N Kariya, A Fukuoka, T Utagawa, M Sakuramoto, Y Goto, M Ichikawa
    APPLIED CATALYSIS A-GENERAL 247 2 247 - 259 2003年07月 [査読有り][通常論文]
     
    Highly efficient production of hydrogen without CO2 emission is achieved in the dehydrogenation of cyclic hydrocarbons under a non-steady spray pulse operation over supported Pt and Pt-M (M = Re, Rh, Pd) catalysts. Cyclohexane, methylcyclohexane, tetralin and decalin were efficiently dehydrogenated by the Pt-containing catalysts supported on thin active carbon cloth (CFF-1500S) sheets and alumite (anodized aluminum) plates. Production rate of hydrogen under the spray pulse mode is higher than the conventional batch-type liquid phase reaction and the steady state gas phase reaction in the flow system. The highest rate, 3800 mmol g(Pt)(-1) min(-1), was obtained in the dehydrogenation of cyclohexane over Pt/alumite heated at 375 degreesC and cyclohexane feed of 190 mmol min(-1) with 3.5 mmol pulse at 1.0 s interval. Bimetallic Pt-Rh/CFF-1500S catalyst showed a higher activity than monometallic Pt/CFF-1500S. Production rate of hydrogen is greatly dependent on the rate of reactant feed, the reaction temperature, and the support. Retardation by products adsorbed on the catalysts was negligible under the spray-pulse operation. (C) 2003 Elsevier Science B.V. All rights reserved.
  • H Araki, A Fukuoka, Y Sakamoto, S Inagaki, N Sugimoto, Y Fukushima, M Ichikawa
    JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL 199 1-2 95 - 102 2003年05月 [査読有り][通常論文]
     
    Template synthesis of gold nano-wire and -particle onto mesoporous silica FSM-16 (Au/FSM-16) has been studied. Several Au/FSM-16 samples were prepared by chemical vapor deposition (CVD) or impregnation methods with subsequent reduction procedures. Organogold complex, dimethyl(hexafluoroacetylacetoato)gold(III) AuMe2(HFA), was adsorbed on FSM-16 by CVD, then irradiated by UV light, leading to the formation of Au nano-wires (diameter, 2.5 nm; mean length, 17.1 nm) in one-dimensional channels of FSM-16 (pore diameter, 2.7 nm). On the other hand, HAuCl4 in aqueous solutions at various pH's was impregnated on FSM-16. The impregnated sample Au3+/FSM-16 prepared at pH 5 was reduced by H-2 at 673 K to give a mixture of An nano-wires and -particles. In contrast, H-2-reduction of Au3+/FSM-16 impregnated at pH 10 only gave homogeneously dispersed Au nano-particles in FSM-16 (mean diameter 1.7 nm). The size and morphology of the nanostructured Au metal is changed by pH of the aqueous HAuCl4 solutions. The Au nano-wires and -particles were characterized by physicochemical methods such as TEM, XRD, EXAFS, and diffuse-reflectance UV-visible. CO oxidation was performed as a catalytic test reaction for the Au/FSM-16 composites. (C) 2003 Elsevier Science B.V. All rights reserved.
  • PL Dhepe, A Fukuoka, M Ichikawa
    CHEMICAL COMMUNICATIONS 5 590 - 591 2003年 [査読有り][通常論文]
     
    RhPt alloy catalysts were prepared in mesoporous silica using supercritical carbon dioxide in impregnation to achieve high dispersion with controlled morphology; catalytic activity and ethane selectivity are enhanced in butane hydrogenolysis.
  • N Kariya, A Fukuoka, M Ichikawa
    CHEMICAL COMMUNICATIONS 6 690 - 691 2003年 [査読有り][通常論文]
     
    High performance (open circuit voltage = 920 mV, maximum power density = 14-15 mW cm(-2)) of the PEM fuel cell was achieved by using cyclohexane as a fuel with zero-CO2 emission and lower-crossover through PEM than with a methanol-based fuel cell.
  • 歌川 忠, 桜元 正, 須貝 保徳, 仮屋 伸子, 福岡 淳, 市川 勝
    日本エネルギー学会大会講演要旨集 12 284 - 285 一般社団法人日本エネルギー学会 2003年
  • 仮屋 伸子, 福岡 淳, 市川 勝
    日本エネルギー学会大会講演要旨集 12 354 - 355 一般社団法人日本エネルギー学会 2003年
  • A Fukuoka, Y Sakamoto, H Araki, S Inagaki, N Sugimoto, Y Fukushima, M Ichikawa
    SCIENCE AND TECHNOLOGY IN CATALYSIS 2002 145 173 - 176 2003年 [査読有り][通常論文]
     
    Pt, Rh, Pt-Rh, and Pt-Pd nanowires were synthesized by a photoreduction method using mesoporous silicas FSM-16 and HMM-1 as templates. The metal nanowires occluded in the mesopores were characterized by several physicochemical methods. The TEM and XAFS studies have demonstrated that the nanowires grow by the reduction of Pt precursors on small nanoparticles initially formed in the mesopores. Dissolution of silica matrix with HF separated the nanowires that are stabilized in solutions. The Pt nanowires and nanoparticles in FSM-16 were used as catalysts in water-gas-shift reaction and hydrogenolysis of butane. It is noteworthy that Pt nanowire/FSM-16 shows higher activities than Pt nanoparticle/FSM-16.
  • A Fukuoka, Y Sakamoto, H Araki, N Sugimoto, S Inagaki, Y Fukushima, M Ichikawa
    NANOTECHNOLOGY IN MESOSTRUCTURED MATERIALS 146 23 - 28 2003年 [査読有り][通常論文]
     
    Several monometallic and bimetallic nanowires of transition metals were synthesized by a photoreduction method using mesoporous silicas FSM-16 and HMM-1 as templates. The metal nanowires were characterized by physicochemical methods such as TEM, XRD, XAFS, XPS, IR, and gas adsorption. Mechanism for formation of Pt nanowires is discussed in terms of relative rates of migration and reduction of Pt ions in the one-dimensional channels. Dissolving silica matrix with HF gave unsupported nanowires, and in the presence of surfactants or ligands the nanowires were stabilized in solutions. The catalytic performances of Pt nanowires and nanoparticles in FSM-16 were studied in water-gas-shift reaction and hydrogenolysis of butane. It is noteworthy that Pt nanowire/FSM-16 shows higher activities than Pt nanoparticle/FSM-16 in both the reactions.
  • N Kariya, A Fukuoka, M Ichikawa
    CHEMICAL COMMUNICATIONS 9 6 690 - 691 2003年 [査読有り][通常論文]
     
    High performance (open circuit voltage = 920 mV, maximum power density = 14-15 mW cm(-2)) of the PEM fuel cell was achieved by using cyclohexane as a fuel with zero-CO2 emission and lower-crossover through PEM than with a methanol-based fuel cell.
  • A Fukuoka, Y Sakamoto, H Araki, S Inagaki, N Sugimoto, Y Fukushima, M Ichikawa
    SCIENCE AND TECHNOLOGY IN CATALYSIS 2002 145 173 - 176 2003年 [査読有り][通常論文]
     
    Pt, Rh, Pt-Rh, and Pt-Pd nanowires were synthesized by a photoreduction method using mesoporous silicas FSM-16 and HMM-1 as templates. The metal nanowires occluded in the mesopores were characterized by several physicochemical methods. The TEM and XAFS studies have demonstrated that the nanowires grow by the reduction of Pt precursors on small nanoparticles initially formed in the mesopores. Dissolution of silica matrix with HF separated the nanowires that are stabilized in solutions. The Pt nanowires and nanoparticles in FSM-16 were used as catalysts in water-gas-shift reaction and hydrogenolysis of butane. It is noteworthy that Pt nanowire/FSM-16 shows higher activities than Pt nanoparticle/FSM-16.
  • A Fukuoka, Y Sakamoto, H Araki, N Sugimoto, S Inagaki, Y Fukushima, M Ichikawa
    NANOTECHNOLOGY IN MESOSTRUCTURED MATERIALS 146 23 - 28 2003年 [査読有り][通常論文]
     
    Several monometallic and bimetallic nanowires of transition metals were synthesized by a photoreduction method using mesoporous silicas FSM-16 and HMM-1 as templates. The metal nanowires were characterized by physicochemical methods such as TEM, XRD, XAFS, XPS, IR, and gas adsorption. Mechanism for formation of Pt nanowires is discussed in terms of relative rates of migration and reduction of Pt ions in the one-dimensional channels. Dissolving silica matrix with HF gave unsupported nanowires, and in the presence of surfactants or ligands the nanowires were stabilized in solutions. The catalytic performances of Pt nanowires and nanoparticles in FSM-16 were studied in water-gas-shift reaction and hydrogenolysis of butane. It is noteworthy that Pt nanowire/FSM-16 shows higher activities than Pt nanoparticle/FSM-16 in both the reactions.
  • PL Dhepe, A Fukuoka, M Ichikawa
    CHEMICAL COMMUNICATIONS 9 5 590 - 591 2003年 [査読有り][通常論文]
     
    RhPt alloy catalysts were prepared in mesoporous silica using supercritical carbon dioxide in impregnation to achieve high dispersion with controlled morphology; catalytic activity and ethane selectivity are enhanced in butane hydrogenolysis.
  • K Umakoshi, T Yamasaki, A Fukuoka, H Kawano, M Ichikawa, M Onishi
    INORGANIC CHEMISTRY 41 16 4093 - 4095 2002年08月 [査読有り][通常論文]
     
    Treatment of pyridine-2-thiol (pytH) with H-2 (60 atm) in the presence of 5-methylpyridine-2-thiolate (5-mpyt)-bridged dinuclear Pt(III), Pt(II), or Pd(II) complexes (1 mol %) in DMF at 150 C for 72 h leads to the formation of pyridine in 3-51% yield. From the H-1 NMR study of the exchange reactions and of the products under D-2 pressure, it is suggested that the catalytic reaction involves bimetallic activation of the pyt ligand followed by the liberation of pyridine and H2S.
  • A Fukuoka, H Araki, Y Sakamoto, N Sugimoto, H Tsukada, Y Kumai, Y Akimoto, M Ichikawa
    NANO LETTERS 2 7 793 - 795 2002年07月 [査読有り][通常論文]
     
    Mesoporous silica films work as templates to form uniform nanoparticles of Au and Pt. The composite materials form an array of metal nanoparticles (diameter ca. 2.5 nm) in the one-dimensional mesopores (pore diameter 2.7 nm), showing an ordered structure in the TEM observation. The nanoparticles are isolated from the silica film by dissolving with a diluted HF solution, and in the presence of 1-dodecanethiol unsupported Au nanoparticles form a superlattice structure.
  • PL Dhepe, A Fukuoka, M Ichikawa
    CATALYSIS LETTERS 81 1-2 69 - 75 2002年07月 [査読有り][通常論文]
     
    Supported Rh catalysts on FSM-16 were prepared by treating FSM-16, impregnated with [Rh(OAc)(2)](2) in supercritical carbon dioxide at 398 K and 30.3 MPa, followed by calcination and hydrogen reduction. The resulting Rh/FSM-16 catalysts were characterized by CO chemisorption, XRD, TEM, FTIR and EXAFS, and catalytic performances of the Rh/FSM-16 were tested in butane hydrogenolysis reaction. It is demonstrated that highly dispersed Rh particles are obtained by the supercritical CO2 treatment. In the hydrogenolysis reactions, the supercritical CO2-treated catalyst showed higher conversions and ethane formation.
  • N Kariya, A Fukuoka, M Ichikawa
    APPLIED CATALYSIS A-GENERAL 233 1-2 91 - 102 2002年07月 [査読有り][通常論文]
     
    Highly efficient evolution of hydrogen is achieved in the dehydrogenation of cycloalkanes such as cyclohexane, methylcyclohexane, and decalin over Pt catalyst supported on active carbon (AC) under "wet-dry multiphase conditions". Formation rate of hydrogen is largely dependent on reaction conditions such as reactant/catalyst ratio, temperature, and support, The highest initial rate of formation of hydrogen, k = 8.0 x 10(-3) mol min(-1), was obtained in the dehydrogenation of cyclohexane over Pt/AC at 623 K and the reactant/catalyst ratio = 3.3 ml g(-1). The addition of second metals such as Mo, W, Re, Rh, Ir, and Pd on the carbon-supported Pt catalysts enhances the dehydrogenation rate due to the promotion of C-H bond cleavage and/or desorption of aromatic products. A physical mixture of Pt/AC and Pd/AC catalysts exhibits higher activities than the monometallic PUAC catalyst owing to the synergistic effects of spillover, migration, and recombination of hydrogen over Pt and Pd catalysts. (C) 2002 Elsevier Science B.V. All rights reserved.
  • 鈴木 教之, YU Jian, 仲村 高志, 福岡 淳
    高分子論文集 59 4 218 - 223 高分子学会 2002年04月25日 [査読無し][通常論文]
  • 五藤 靖志, 歌川 忠, 桜元 正, 須貝 保徳, 仮屋 伸子, 福岡 淳, 市川 勝
    日本エネルギー学会大会講演要旨集 80 238 - 239 一般社団法人日本エネルギー学会 2002年
  • 歌川 忠, 桜元 正, 須貝 保徳, 五藤 靖志, 仮屋 伸子, 福岡 淳, 市川 勝
    日本エネルギー学会大会講演要旨集 80 236 - 237 一般社団法人日本エネルギー学会 2002年
  • A Fukuoka, N Higashimoto, Y Sakamoto, S Inagaki, Y Fukushima, M Ichikawa
    TOPICS IN CATALYSIS 18 1-2 73 - 78 2002年 [査読無し][通常論文]
     
    Pt nanowires are prepared in mesoporous FSM-16 by photoreduction of H2PtCl6, while H-2-reduction of H2PtCl6/FSM-16 at 673 K gives Pt nanopatrticles in FSM-16. The Pt nanowires and nanoparticles are characterized by physicochemical methods such as XAFS, TEM, XRD, and XPS. The formation mechanism of the Pt nanowires and the catalytic performance in the water-gas-shift reaction are also investigated.
  • N Suzuki, J Yu, N Shioda, H Asami, T Nakamura, T Huhn, A Fukuoka, M Ichikawa, M Saburi, Y Wakatsuki
    APPLIED CATALYSIS A-GENERAL 224 1-2 63 - 75 2002年01月 [査読有り][通常論文]
     
    Novel methodology was developed for preparation of isospecific metallocene catalysts for olefin polymerization that are tethered on silica surfaces with covalent bonds. A racemic ansa-zirconocene complex that has a Si-Cl moiety on its bridge was immobilized on SiO2 by the reaction of the Si-Cl anchor with Si-OH on the solid surface, The prepared solid catalyst was found to be effective for isospecific propene polymerization (catalyst A). Pretreatment of silica surfaces with Me3SiCl improved the catalyst performance (catalyst B). An ansa-zirconocene complex with a BH group reacted with "vinyl-coated" silica gel to afford another immobilized catalysts (catalyst C). This catalyst achieved satisfactorily high catalytic activity and high isotacticity in its produced polypropene. (C) 2002 Elsevier Science B.V. All rights reserved.
  • N Suzuki, J Yu, T Nakamura, A Fukuoka
    KOBUNSHI RONBUNSHU 59 4 218 - 223 2002年 [査読無し][通常論文]
     
    A group 4 metallocene complex that serves as olefin polymerization catalyst was tethered on a solid support such as silica gel by covalent bonds. A zirconocene complex that has a vinyl group on its cyclopentadienyl ligand was hydrosilated or hydroborated to introduce a functional anchor for immobilization reactions. The complex with a Si-Cl group was tethered on a silica surface by the reaction with a surface Si-OH group. The zirconocene with a BH group was immobilized on a silica gel modified with chlorodimethylvinylsilane. Ethylene polymerization using the tethered catalysts, showed that the hydroboration-method seems more effective than the hydrosilation-method, It exhibited comparable catalytic activity to the corresponding homogeneous catalyst and produced polyethylene of a higher molecular weight.
  • A Fukuoka, N Higashimoto, Y Sakamoto, S Inagaki, Y Fukushima, M Ichikawa
    TOPICS IN CATALYSIS 18 1-2 73 - 78 2002年 [査読有り][通常論文]
     
    Pt nanowires are prepared in mesoporous FSM-16 by photoreduction of H2PtCl6, while H-2-reduction of H2PtCl6/FSM-16 at 673 K gives Pt nanopatrticles in FSM-16. The Pt nanowires and nanoparticles are characterized by physicochemical methods such as XAFS, TEM, XRD, and XPS. The formation mechanism of the Pt nanowires and the catalytic performance in the water-gas-shift reaction are also investigated.
  • N Suzuki, J Yu, T Nakamura, A Fukuoka
    KOBUNSHI RONBUNSHU 59 4 218 - 223 2002年 [査読有り][通常論文]
     
    A group 4 metallocene complex that serves as olefin polymerization catalyst was tethered on a solid support such as silica gel by covalent bonds. A zirconocene complex that has a vinyl group on its cyclopentadienyl ligand was hydrosilated or hydroborated to introduce a functional anchor for immobilization reactions. The complex with a Si-Cl group was tethered on a silica surface by the reaction with a surface Si-OH group. The zirconocene with a BH group was immobilized on a silica gel modified with chlorodimethylvinylsilane. Ethylene polymerization using the tethered catalysts, showed that the hydroboration-method seems more effective than the hydrosilation-method, It exhibited comparable catalytic activity to the corresponding homogeneous catalyst and produced polyethylene of a higher molecular weight.
  • A Fukuoka, N Higashimoto, Y Sakamoto, S Inagaki, Y Fukushima, M Ichikawa
    MICROPOROUS AND MESOPOROUS MATERIALS 48 1-3 171 - 179 2001年11月 [査読有り][通常論文]
     
    Pt and Rh nanowires and/or particles were prepared in mesopores of FSM-16, and their characterization and catalytic performances were investigated. Irradiation of UV-Vis light to FSM-16 (pore size 2.7 nm) impregnated with H2PtCl6 in the presence of water and 2-propanol (or methanol) vapors led to the formation of Pt nanowires (diameter 2.5 nm. length 50-300 nm) in the mesopores of FSM-16. In contrast, H-2-reduction of H2PtCl6/FSM-16 at 673 K for 2 h resulted in the formation of Pt nanoparticles in FSM-16. The XANES and XPS studies show that the Pt wires and particles are slightly electron-deficient, implying the interaction with the internal surface of mesopore. At the initial stage of the formation of Pt wires, it is found that small Pt nanoparticles are formed in the mesopores. Then Pt ions migrate and are reduced on the surface of the small particles, thus resulting in the formation of the Pt nanowires. Rh nanoparticles were prepared in FSM-16 by calcination of RhCl3/FSM-16 at 673 K and subsequent H-reduction at 473 K. Furthermore, nanowires (diameter 2.5 urn, length 10-50 nm) were formed in FSM-16 by the similar photoreduction of the FSM-16 co-impregnated with H2PtCl6 and RhCl3, In hydrogenolysis of butane, Pt nanowire/FSM-16 exhibits higher catalytic activities than Pt nanoparticle/FSM-16, while Pt-Rh nanowire/FSM-16 shows high activity of isomerization to isobutane. (C) 2001 Elsevier Science B.V.. All rights reserved.
  • PPHJM Knops-Gerrits, A Fukuoka, WA Goddard
    JOURNAL OF INORGANIC BIOCHEMISTRY 86 1 297 - 297 2001年08月 [査読有り][通常論文]
  • A Fukuoka, S Fukagawa, M Hirano, N Koga, S Komiya
    ORGANOMETALLICS 20 10 2065 - 2075 2001年05月 [査読有り][通常論文]
     
    A series of Pd-containing heterodinuclear methyl complexes, (dppe)(CH3)Pd-ML, (ML, MoCp(CO)(3), WCp(CO)(3), Co(CO)(4); dppe = 1,2-bis(diphenylphosphino)ethane), have been prepared by the metathetical reactions of Pd(CH3)(NO3)(dppe) with Na+[MLn](-), and the complexes were characterized by spectroscopic methods and/or X-ray structure analysis. Related Pt-containing dinuclear complexes were similarly prepared and characterized. The rate of CO insertion into a Pd-CH3 or Pt-CH3 bond was investigated using these complexes. The Pd-Co complex (dppe)(CH3)Pd-Co(CO)4 shows a high activity of CO insertion, giving (dppe)(CH3CO)Pd-Co(CO)(4), and the initial rate is ca. 80 times higher than those of the analogous complex Pd(CH3)Cl(dppe). Whereas slow insertion of CO is observed in the Pt-Co complex (dppe)(CH3)Pt-Co(CO)(4), no reaction takes place for Pt(CH3)Cl(dppe). It is revealed by using (CO)-C-13 that CO in the Co(CO)(4) fragment preferentially inserts into the PdCH3 bond over CO in the gas phase. The carbonyl insertion reaction in the Pd-Co heterodinuclear complex has been theoretically studied using B3LYP hybrid density functional theory to clarify its reaction mechanism and the electronic factors controlling the reaction. The calculations for a model complex, (H2PCH2CH2PH2)Pd(CH3)-Co(CO)(4), have shown that the most favorable reaction path consists of methyl migration from the Pd to the Co atom, carbonyl insertion reaction on the Co atom, CO coordination to the Co atom, and acetyl migration from the Co atom to the Pd atom, which is in accord with the experimental results. The electron donation from the Pd d orbital to the bridging CO pi* orbitals plays an important role in stabilizing the intermediates and transition states.
  • A Fukuoka, Y Sakamoto, S Guan, S Inagaki, N Sugimoto, Y Fukushima, K Hirahara, S Iijima, M Ichikawa
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 123 14 3373 - 3374 2001年04月 [査読有り][通常論文]
  • A Fukuoka, N Higashimoto, Y Sakamoto, M Sasaki, N Sugimoto, S Inagaki, Y Fukushima, M Ichikawa
    CATALYSIS TODAY 66 1 23 - 31 2001年03月 [査読有り][通常論文]
     
    Ship-in-bottle synthesis of platinum carbonyl clusters, nanowires, and nanoparticles in micro- and mesoporous materials is described. Reductive carbonylation of Pt ions impregnated on NaY zeolite or on mesoporous silica FSM-16 leads to the selective formation of the Chini-type Pt carbonyl clusters. Decarbonylation of the resulting clusters yields naked Pt nanoparticles (diameter 1.0-1.5 nm) in NaY or in FSM-16. Similar Pt nanoparticles in FSM-16 are prepared by the direct hydrogen reduction of H2PtCl6/FSM-16 at 673 K, and in this case Pt particles in size of 2.5 nm are formed in the mesopores of FSM-16 (pore size 2.7 nm). In contrast, Pt nanowires (diameter 2.5 nm, length 50-300 nm) are obtained by the photoreduction of H2PtCl6/FSM-16 in the presence of vapors of water and 2-propanol. The Pt nanowires exhibit unique properties in CO chemisorption and magnetism due to their morphology in the mesoporous channels of FSM-16. In the water-gas-shift reaction, Pt nanowire/FSM-16 shows a higher catalytic activity than that of Pt nanoparticle/FSM-16. The Pt nanowires are chemically extracted from the mesopores using [NBu4]Cl in a mixture of benzene and ethanol. (C) 2001 Elsevier Science B.V. All rights reserved.
  • A Fukuoka, N Higashimoto, Y Sakamoto, M Sasaki, N Sugimoto, S Inagaki, Y Fukushima, M Ichikawa
    CATALYSIS TODAY 66 1 23 - 31 2001年03月 [査読有り][通常論文]
     
    Ship-in-bottle synthesis of platinum carbonyl clusters, nanowires, and nanoparticles in micro- and mesoporous materials is described. Reductive carbonylation of Pt ions impregnated on NaY zeolite or on mesoporous silica FSM-16 leads to the selective formation of the Chini-type Pt carbonyl clusters. Decarbonylation of the resulting clusters yields naked Pt nanoparticles (diameter 1.0-1.5 nm) in NaY or in FSM-16. Similar Pt nanoparticles in FSM-16 are prepared by the direct hydrogen reduction of H2PtCl6/FSM-16 at 673 K, and in this case Pt particles in size of 2.5 nm are formed in the mesopores of FSM-16 (pore size 2.7 nm). In contrast, Pt nanowires (diameter 2.5 nm, length 50-300 nm) are obtained by the photoreduction of H2PtCl6/FSM-16 in the presence of vapors of water and 2-propanol. The Pt nanowires exhibit unique properties in CO chemisorption and magnetism due to their morphology in the mesoporous channels of FSM-16. In the water-gas-shift reaction, Pt nanowire/FSM-16 shows a higher catalytic activity than that of Pt nanoparticle/FSM-16. The Pt nanowires are chemically extracted from the mesopores using [NBu4]Cl in a mixture of benzene and ethanol. (C) 2001 Elsevier Science B.V. All rights reserved.
  • K Fujishima, A Fukuoka, A Yamagishi, S Inagaki, Y Fukushima, M Ichikawa
    JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL 166 2 211 - 218 2001年02月 [査読有り][通常論文]
     
    Catalytic performances of bis- and tris(bipyridine) Ru complexes grafted on mesoporous FSM-16 were studied in the photooxidation of benzene to phenol using H(2)O(2) as an oxidant, [Ru(bpy)(3)]Cl(2)/FSM-16 showed a high activity under W-irradiation, and the turnover number (TON) of phenol was 430 based on Ru in 24 h, and the selectivity to phenol among the products was 98%. Non-grafted [Ru(bpy)(3)]Cl(2) complex gave a phenol TON of 170, thus demonstrating the promotion effect of grafting [Ru(bpy)(3)]Cl(2) on FSM-16. The hydroxylation of benzene to phenol by [Ru(bpy)(3)]Cl(2) on FSM-16 slightly occurred in the dark (TON = 34 in 24 h), but the irradiation remarkably increased the TON of phenol by a factor of 13. The absorption peak of [Ru(bpy)(3)]Cl(2) in the UV-VIS spectroscopy decreased under the reaction conditions; however, the recovered catalyst showed almost the same activity for phenol formation in the repeated runs. It is proposed that coodinatively unsaturated [Ru(bpy)(n)](2+) (n = 1,2) are generated by the UV-irradiation to [Ru(bpy)(3)]Cl(2) on FSM-16. These species activate H(2)O(2) to give an OH radical that attacks benzene as in the Fenton-type mechanism. Grafting of the Ru complex on FSM-16 may enhance the reaction of a hydroxycyclohexadienyl radical with the isolated Ru center. (C) 2001 Elsevier Science B.V. All rights reserved.
  • PP Knops-Gerrits, PA Jacobs, A Fukuoka, M Ichikawa, F Faglioni, WA Goddard
    JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL 166 1 3 - 13 2001年01月 [査読有り][通常論文]
     
    Methane mono-oxygenase (MMO) and deoxyhemerythrin (DHr) are examples of di-iron enzymes that catalyze the dissociative and non-dissociative binding of molecular oxygen. To mimic the MMO active site with a finite cluster, we chose to study the binuclear heptapodate coordinated iron(III)-complexes of N,N,N,N'-tetrakis(2-benzimidazolylmethyl)-2-hydroxy-1,3-diamino-propane (HPTB) and N,N,N',N'-tetrakis(2-pyridylmethyl)-2-hydroxy-1,3-diamino-propane (HPTP). These have active sites of the form [Fez (HPTP)(mu -OH)](4+) (1) and [Fe-2(HPTB)(mu -OH)](4+) (2). Quantum mechanics structures are compared with the experimental data obtained from the EXAFS analysis. For the O-2 binding on the reduced active site. the mu-eta (1):eta (1)-O-2 mode seems the slightly more stable precursor to the O=Fe-O-Fe=O bis-ferryl (re)active site. The nature of the ferryl groups are these of a reactive two center three electron bond. (C) 2001 Elsevier Science B.V. All rights reserved.
  • A. Fukuoka, Y. Sakamoto, S. Inagaki, N. Sugimoto, Y. Fukushima, M. Ichikawa
    Studies in Surface Science and Catalysis 135 169  2001年 [査読有り][通常論文]
     
    Template synthesis of transition metal nanowires in mesoporous materials was performed. Pt, Rh, Pt-Rh, and Pt-Pd nanowires were synthesized in HMM-1 and FSM-16 using photoreduction method. The bimetallic nanowires in HMM-1 were alloy crystallite with a necklace-like structure. Pt-Pd wire/HMM-1 exhibited higher magnetic susceptibility at low temperature than the Pt wire. In butane hydrogenolysis, Pt-Rh wire/FSM-16 showed high selectivity to isobutane. This is an abstract of a paper presented at the 13th International Zeolite Conference (Montpellier, France 7/8-13/2001).
  • Sanshiro Komiya, Toshiyuki Yasuda, Atsushi Fukuoka, Masafumi Hirano
    Journal of Molecular Catalysis A: Chemical 159 1 63 - 70 2000年09月 [査読有り][通常論文]
     
    Hydridoplatinum-molybdenum (or tungsten) heterodinuclear complexes (dppe)HPt-MCp(CO)3 [M = Mo (1), W (2); dppe = 1,2-bis(diphenylphosphino)ethane] have been prepared by selective β-hydrogen elimination of corresponding ethylplatinum-molybdenum (or tungsten) complexes (dppe)EtPt-MCp(CO)3 [M = Mo (3), W (4)]. The β-hydrogen elimination process is significantly facilitated by electron-withdrawing transition metal ligand at platinum such as Co(CO)4 (5). Acetylenes having electron withdrawing groups induce selective hydride transfer reaction in these heterodunucelar complex 1-2 to give hydridomolybdenum (or tungsten) and zero-valent (acetylene)platinum complexes. (C) 2000 Elsevier Science B.V.
  • K Zama, Y Imada, A Fukuoka, M Ichikawa
    APPLIED CATALYSIS A-GENERAL 194 285 - 296 2000年03月 [査読有り][通常論文]
     
    Some polynuclear molybdenum complexes such as Mo(2)(OAC)(4), Mo(2)(OBu(t))(4), [Mo(3)O(CCH(3))(OAc)(6)(CH(3)OH)(3)]Cl, and [(RhCp*)(4)Mo(4)O(16)] grafted with silica and mesoporous channels of FSM-16 were investigated for their structural characterization and catalytic performances in propane metathesis reaction. It was demonstrated by ESR, FT-IR, and EXAFS studies that Mo(2)(OAc)(4) grafted on FSM-16 while keeping a dinuclear Mo-Mo unit by a partial removal of the acetate ligand at 623 K, resulting in the formation of mixed valent dinuclear species [Mo-Mo](V) characteristic of an intense ESR signal (g = 1.926) and EXAFS parameters (R (Mo-Mo) = 2.11 Angstrom coordination number = 0.6), similar to those grafted on silica, The resulting Mo dimer species-grafted on FSM-16 exhibited a high activity in propene metathesis to yield ethene and 2-butenes. On the other hand, FT-IR, TPD/MS and EXAFS studies revealed that [Mo(3)O(CCH(3))(OAc)(6)(CH(3)OH)]Cl on FSM-16was transformed by pyrolysis at 573 K to Mo trinuclear species which is active for propene metathesis. The relative activities of surface-grafted Mo species grafted on FSM-16 were measured as the following order with the;respect to molybdenum nuclearity of the precursor complexes; Mo(2) (4100) > Mo(3) (110) > Mo(4) (7.3) much greater than Mo(7) O(24)(2-) (0.3), where the numbers in parentheses denote TOF (h(-1)). The exceeding thermal treatment above 673-723 K for the active Mo(2) and Mo(3) species causes the complete cleavage of the Mo-Mo bond to give highly dispersed MoO(3) on silica and FSM-16, which is inactive for propene metathesis. By contrast to silica and FSM-16, the Mo(2) and Mo(3) catalysts prepared on Al(2)O(3), MgO and NaY are inactive for propene metathesis. (C) 2000 Elsevier Science B.V. All rights reserved.
  • K Zama, A Fukuoka, Y Sasaki, S Inagaki, Y Fukushima, M Ichikawa
    CATALYSIS LETTERS 66 4 251 - 253 2000年 [査読有り][通常論文]
     
    Mo complexes with Mo(1)-Mo(4) nuclearities were grafted on mesoporous silica FSM-16, and their catalytic performances were studied in the hydroxylation of benzene. A trinuclear Mo oxo complex grafted on FSM-16 exhibits the highest catalytic activity in the hydroxylation of benzene to phenol using hydrogen peroxide as an oxidant under the irradiation of UV-light. The turnover numbers for phenol are over 700 at 300 K.
  • A Fukuoka, K Fujishima, M Chiba, A Yamagishi, S Inagaki, Y Fukushima, M Ichikawa
    CATALYSIS LETTERS 68 3-4 241 - 244 2000年 [査読有り][通常論文]
     
    Fullerenes (C-60 and C-70) are grafted on mesoporous FSM-16 (pore size 2.7 nm), and the grafted fullerenes showed high activities (TON up to 3070 in 9 h) for allylic oxidation of cyclohexene with oxygen in benzene under the irradiation of UV-vis light. In these reactions, phenol is also formed by the oxidation of benzene with cyclohexene hydroperoxide produced in the allylic oxidation of cyclohexene.
  • Fukuoka A, Higashimoto N, Sasaki M, Harada M, Inagaki S, Fukushima Y, Ichikawa M
    Studies in Surface Science and Catalysis 130 C 3041 - 3046 2000年 [査読有り][通常論文]
  • K Zama, A Fukuoka, Y Sasaki, S Inagaki, Y Fukushima, M Ichikawa
    CATALYSIS LETTERS 66 4 251 - 253 2000年 [査読有り][通常論文]
     
    Mo complexes with Mo(1)-Mo(4) nuclearities were grafted on mesoporous silica FSM-16, and their catalytic performances were studied in the hydroxylation of benzene. A trinuclear Mo oxo complex grafted on FSM-16 exhibits the highest catalytic activity in the hydroxylation of benzene to phenol using hydrogen peroxide as an oxidant under the irradiation of UV-light. The turnover numbers for phenol are over 700 at 300 K.
  • A Fukuoka, K Fujishima, M Chiba, A Yamagishi, S Inagaki, Y Fukushima, M Ichikawa
    CATALYSIS LETTERS 68 3-4 241 - 244 2000年 [査読有り][通常論文]
     
    Fullerenes (C-60 and C-70) are grafted on mesoporous FSM-16 (pore size 2.7 nm), and the grafted fullerenes showed high activities (TON up to 3070 in 9 h) for allylic oxidation of cyclohexene with oxygen in benzene under the irradiation of UV-vis light. In these reactions, phenol is also formed by the oxidation of benzene with cyclohexene hydroperoxide produced in the allylic oxidation of cyclohexene.
  • Fujishima K, Fukuoka A, Ichikawa M
    Studies in Surface Science and Catalysis 130 B 1979 - 1984 2000年 [査読有り][通常論文]
  • A Fukuoka, A Sato, K Kodama, M Hirano, S Komiya
    INORGANICA CHIMICA ACTA 294 2 266 - 274 1999年11月 [査読有り][通常論文]
     
    A series of organosiloxo complexes of platinum and palladium, MR(OSiPh3)(L-2) (M = Pt, Pd; R = Me, Et, Ph; L-2 = cod, dppe), has been prepared and characterized. The square planar geometries of PtPh(OSiPh3)(cod) and PtEt(OSiPh3)(cod) are confirmed by X-ray structure analysis. In the reactions with hydrogen at 0 degrees C and 1 atm, the siloxo complexes of Pt and Pd are reduced readily to give agglomerates of nanoclusters with complete hydrogenation of the ligands. The reduction activities of the siloxo and alkoxo complexes are higher than those of the corresponding alkyl complex PtMed(2)(cod). This high activity in reduction is applied to the preparation of supported Pt or Pd nanoclusters on silica, and the siloxo complexes adsorbed on silica are reacted with hydrogen at mild conditions. The resulting Pt/SiO2 gives a smaller mean diameter than that prepared from H2PtCl6/SiO2. (C) 1999 Elsevier Science S.A. All rights reserved.
  • A Fukuoka, M Osada, T Shido, S Inagaki, Y Fukushima, M Ichikawa
    INORGANICA CHIMICA ACTA 294 2 281 - 284 1999年11月 [査読有り][通常論文]
     
    Mesoporous channels (2.7 and 4.7 nm pore size) of FSM-16 were modified with titania or zirconia by the impregnation and hydrolysis of Ti or Zr alkoxides with subsequent calcination. Platinum carbonyl clusters [Pt(3)(CO)(6)](n)(2-) (n = 4-6) were synthesized in the modified FSM-16 by the reaction of H(2)PtCl(6) with CO and H(2)O at 323 K, and the clusters were characterized by IR and UV-Vis spectroscopies. Evacuation of the Pt carbonyl clusters at 573 K gave nanoparticles in FSM-16, and the resulting Pt/TiO(2), (or ZrO(2))/FSM-16 catalysts showed higher CO conversions and selectivities to C(2)-C(3) alkanes in CO hydrogenation than the unmodified Pt/FSM-16. (C) 1999 Elsevier Science S.A. All rights reserved.
  • R Doumeki, M Hatano, H Kinoshita, E Yamashita, M Hirano, A Fukuoka, S Komiya
    CHEMISTRY LETTERS 6 515 - 516 1999年06月 [査読有り][通常論文]
     
    Selective catalytic reduction of NO by C3H6 has been studied for supported Pt catalysts prepared from organoplatinum complexes and an inorganic platinum salt. N-2/N2O selectivity is improved by using the organoplatinum complexes as precursors at similar maximum conversions of NOx to N-2 and N2O for the catalysts tested.
  • R Doumeki, M Hatano, H Kinoshita, E Yamashita, M Hirano, A Fukuoka, S Komiya
    CHEMISTRY LETTERS 6 515 - 516 1999年06月 [査読有り][通常論文]
     
    Selective catalytic reduction of NO by C3H6 has been studied for supported Pt catalysts prepared from organoplatinum complexes and an inorganic platinum salt. N-2/N2O selectivity is improved by using the organoplatinum complexes as precursors at similar maximum conversions of NOx to N-2 and N2O for the catalysts tested.
  • M Sasaki, M Osada, N Higashimoto, T Yamamoto, A Fukuoka, M Ichikawa
    JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL 141 1-3 223 - 240 1999年05月 [査読有り][通常論文]
     
    The robust trigonal prismatic Pt(18) and Pt(15) cluster anions are selectively synthesized via [Pt(CO)Cl(3)](-) in FSWI-16 (4.7 nm) and cis-Pt(CO)(2)Cl(2) in FSM-16 (2.8 nm) by the reductive carbonylation of H(2)PtCl(6) in the confined mesoporous channels of FSM-16, respectively. The Pt cluster anions extracted from the resulting samples in the THF solution by cation metathesis with [PPN]Cl are identified as [Pt(3)(CO)(6)](5)(2-) in FSM-16 (2.8 nm) and [Pt(3)(CO)(6)](5)(2-) in FSM-16 (4.7 nm) by the FTIR and UV-Vis spectroscopic data. The EXAFS and FTIR studies demonstrated that [Pt(3)(CO)(6)](5)(2-)/FSM-16 (2.8 nm) (nu(CO) = 2078, 1880 cm(-1)) and [Pt(3)(CO)(6)](6)(2-)/FSM-16 (4.7 nm) (nu(CO) = 2056, 1879 cm(-1)) were transformed by heating at 300-343 K into the partially decarbonylated Pt clusters (Pt-Pt; C.N. = 7.6, R = 2.73 Angstrom) characteristic of a linear CO band (nu(CO) = 2015 cm(-1)). According to the EXAFS and TEM observation, Pt carbonyl clusters are eventually converted above 473 K to naked Pt particles of 11 Angstrom (Pt-Pt C.N. = 6.7, R = 2.72 Angstrom) in FSM-16 (2.8 MI) and of 15 Angstrom (C.N. = 7.9, R = 2.74 Angstrom) in FSM-16 (4.7 nn). On the other hand, the platinum nanowires [2 and 4 nm (diameter) x 50-500 nm (long)] are prepared using the cylindrical mesoporous channels of FSM-16 (2.8 and 4.7 Mn) in the templating reduction of H(2)PtCl(6) by the exposure to gamma-ray or W-light (lambda(max) > 254 nm) under the atmosphere of 2-propanol and water. It was demonstrated by the TEM observation and EXAFS characterization that the diameters of Pt nanowires formed in FSM-16 are consistent with those of FSM-16 used (2.8 and 4.7 nn), whereas the average lengths of Pt wires are varied by the function of the Pt loading mass and time exposure to gamma-ray and UV-light. The observed electron beam diffraction patterns indicate that the Pt wires consist of a single crystal phase of Pt(110) having a lattice fringe of 2.27 Angstrom. It is of interest to find that the Pt nanowires in FSM-16 (2.8 nm and 4.7 nm) exhibited an unique IR spectrum in CO chemisorption and the remarkable activities per surface Pt atom (TOF) for water gas-shift reaction at 323-393 K by 60-90 times larger than those of Pt nanoparticles in FSM-16 and even conventional metal catalysts. (C) 1999 Elsevier Science B.V. All rights reserved.
  • N Suzuki, H Asami, T Nakamura, T Huhn, A Fukuoka, M Ichikawa, M Saburi, Y Wakatsuki
    CHEMISTRY LETTERS 4 341 - 342 1999年04月 [査読有り][通常論文]
     
    A C-2-symmetric ansa-zirconocene complex which has a Si-Cl moiety on its bridge was immobilized on SiO2 by the reaction of the Si-Cl anchor with Si-OH on the solid surface. The prepared solid catalyst was found to be effective for isospecific propene polymerization. It exhibited higher productivity compared to a catalyst prepared using the zirconocene without a Si-Cl anchor. The effect of pretreatment of silica surfaces with Me3SiCl on catalyst performance is also described.
  • N Suzuki, H Asami, T Nakamura, T Huhn, A Fukuoka, M Ichikawa, M Saburi, Y Wakatsuki
    CHEMISTRY LETTERS 4 341 - 342 1999年04月 [査読有り][通常論文]
     
    A C-2-symmetric ansa-zirconocene complex which has a Si-Cl moiety on its bridge was immobilized on SiO2 by the reaction of the Si-Cl anchor with Si-OH on the solid surface. The prepared solid catalyst was found to be effective for isospecific propene polymerization. It exhibited higher productivity compared to a catalyst prepared using the zirconocene without a Si-Cl anchor. The effect of pretreatment of silica surfaces with Me3SiCl on catalyst performance is also described.
  • A Fukuoka, W Kosugi, F Morishita, M Hirano, L McCaffrey, W Henderson, S Komiya
    CHEMICAL COMMUNICATIONS 6 489 - 490 1999年03月 [査読有り][通常論文]
     
    Novel water-soluble Ir and Rh complexes with tris(hydroxymethyl)phosphine catalyse the selective hydrogenation of the C=O bond of cinnamaldehyde and the hydroformylation of pent-1-ene both under biphasic conditions.
  • RM Deshpande, A Fukuoka, M Ichikawa
    CHEMISTRY LETTERS 1 13 - 14 1999年 [査読無し][通常論文]
     
    A Rh-cyclodextrin phosphinite catalyst exhibits substrate selectivities in hydroformylation of C-8 and C-10 olefins due to the inclusion of substrates in the cyclodextrin cavity.
  • Noriyuki Suzuki, Hayato Asami, Takashi Nakamura, Thomas Huhn, Atsushi Fukuoka, Masaru Ichikawa, Masahiko Saburi, Yasuo Wakatsuki
    Chemistry Letters 4 341 - 342 1999年 [査読無し][通常論文]
     
    A C2-symmetric afwa-zirconocene complex which has a Si-Cl moiety on its bridge was immobilized on SiO2 by the reaction of the Si-Cl anchor with Si-OH on the solid surface. The prepared solid catalyst was found to be effective for isospecific propene polymerization. It exhibited higher productivity compared to a catalyst prepared using the zirconocene without a Si-Cl anchor. The effect of pretreatment of silica surfaces with Me3SiCl on catalyst performance is also described.
  • Reiko Doumeki, Masaharu Hatano, Hiroo Kinoshita, Emi Yamashita, Masafumi Hirano, Atsushi Fukuoka, Sanshiro Komiya
    Chemistry Letters 6 515 - 516 1999年 [査読無し][通常論文]
     
    Selective catalytic reduction of NO by C3H6 has been studied for supported Pt catalysts prepared from organoplatinum complexes and an inorganic platinum salt. N2/N2O selectivity is improved by using the organoplatinum complexes as precursors at similar maximum conversions of NOx to N2 and N2O for the catalysts tested.
  • N Nakahara, M Hirano, A Fukuoka, S Komiya
    JOURNAL OF ORGANOMETALLIC CHEMISTRY 572 1 81 - 85 1999年01月 [査読有り][通常論文]
     
    Sulfur bridged Pt-Ti heterobimetallic complexes, Cp2Ti(mu-SR)(2)PtMe2, (R = Me (1a), Ph (1b)) have been prepared by the reaction of Cp2Ti(SR)(2) with PtMe2(nbd). X-ray structure analysis of la reveals the syn conformation of the compound, while a facile equilibration between syn and anti conformers is observed in toluene solution by variable temperature H-1-NMR. (C) 1999 Elsevier Science S.A. All rights reserved.
  • RM Deshpande, A Fukuoka, M Ichikawa
    CHEMISTRY LETTERS 1 13 - 14 1999年 [査読有り][通常論文]
     
    A Rh-cyclodextrin phosphinite catalyst exhibits substrate selectivities in hydroformylation of C-8 and C-10 olefins due to the inclusion of substrates in the cyclodextrin cavity.
  • S Komiya, A Fukuoka, M Hirano
    SCIENCE AND TECHNOLOGY IN CATALYSIS 1998 121 133 - 138 1999年 [査読有り][通常論文]
     
    Insertion of CO into Pd(or Pt)-C bond in (dpe)MeM-Co(CO)(4) (M = Pd (1), Pt (2)) is faster than that observed in PdMeCl(dpe). C-13 labeling experiment reveals the preferential inserion of the coordinated CO in Co moiety into Pd-C bond to give corresponding acyl derivative. Structural determination of 1 indicates that one of the semi-bridging CO ligand has close contact with Pd. On the other hand, beta-hydrogen elimination reaction in (dpe)EtPt-MoCp(CO)(3) is also accelerated to give corresponding hydride complex, (dpe)HPt-MoCp(CO)(3) and ethylene with retention of the configuration in comparison with PtEtCl(dpe).
  • M Hirano, M Hirai, Y Ito, T Tsurumaki, A Baba, A Fukuoka, S Komiya
    JOURNAL OF ORGANOMETALLIC CHEMISTRY 569 1-2 3 - 14 1998年10月 [査読有り][通常論文]
     
    Enolatorhenium(I) complexes cis-Re(NCCRCO2R')(NCCHRCO2R')(PMe2Ph)(4) (R = H, R' = Me (2a); R = H, R' = Et (2b); R = H, R' = n-Bu (2c); R = Me, R' = Et (2d)) are prepared by the reaction of ReH(N-2)(PMe2Ph)(4) (1) with alkyl cyanoalkyl carboxylate. X-ray structure analysis of 2b shows that it has an octahedral Re geometry, where mutually cis enolato and ester ligands bind to the rhenium via cyano groups. Reaction of 2b with benzaldehyde gives Re(NCCHCO3Et)[NC(EtO2C)C-CHPh]-(PMe2Ph)(4) (4), which is also derived from the ligand exchange reaction of 2b with ethyl (E)-2-cyano-3-phenylpropenoate. These rhenium(I) complexes 1, 2, and 4 catalyze Knoevenagel and Michael reactions under neutral and mild conditions. A possible mechanism for the Knoevenagel reaction has been proposed. (C) 1998 Elsevier Science S.A. All rights reserved.
  • A Fukuoka, T Nagano, S Furuta, M Yoshizawa, M Hirano, S Komiya
    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 71 6 1409 - 1415 1998年06月 [査読有り][通常論文]
     
    Zero-valent ruthenium complexes, [Ru(cod)(cot)] and [Ru(cod)(benzene)], are effective catalyst precursors for the tail-to-tail dimerization of acrylonitrile. Hydrogen pressure is necessary for the catalytic reaction, and the turnover number for dimers is greatly improved in neat acrylonitrile. Under the conditions of 150 degrees C and 25 atm of H-2 (initial pressure at room temperature), the conversion of acrylonitrile is 61% and the yield of tail-to-tail dimers is 42% (selectivity 69%) in 3 h. The turnover number for the dimers is 2060, which is much higher than those reported so far. From the results of a catalytic reaction under D-2 pressure, a reaction mechanism is proposed, in which two successive insertions of acrylonitrile into dihydridoruthenium complex are involved. A fast and reversible insertion of the third acrylonitrile is responsible for the H-D exchange of acrylonitrile in the deuterium labeling experiment.
  • M Sasaki, M Osada, N Sugimoto, S Inagaki, Y Fukushima, A Fukuoka, M Ichikawa
    MICROPOROUS AND MESOPOROUS MATERIALS 21 4-6 597 - 606 1998年05月 [査読有り][通常論文]
     
    The robust trigonal prismatic cluster anions such as [Pt(3)(CO)(6)](5)(2-) and [Pt(3)(CO)(6)](6)(2-) were selectively synthesized in the ordered hexagonal channels (2.8 and 4.7 nm diameter) of FSM-16 and ZrO(2)-modified FSM-16 by a 'ship-in-bottle' technique in the reductive carbonylation of H(2)PtCl(6) with CO+H(2)O at 323 K. The cluster anions were characterized by FTIR, UV-visible, TEM and EXAFS spectroscopy. The Zr oxide-modified FSM-16 was prepared by CVD method using Zr(2-propoxyl)(4) impregnated with FSM-16, followed by calcination at 723 K. The controlled removal of CO from [Pt(3)(CO)(6)](5)(2-) and [Pt(3)(CO)(6)](6)(2-) in FSM-16 by thermal evacuation at 300-423 K yields nanostructured Pt clusters of 1.5-2 nm diameter highly dispersed in the channels of FSM-16. By contrast, Pt nano-wires were prepared by a templating reduction of Pt salts impregnated in FSM-16 (2.8 and 4.7 nm) under photo- and gamma-ray irradiation (see Scheme 1). They exhibited unique properties in CO chemisorption and magnetism due to their anisotropic morphology of Pt nano-wires aligned in the ordered mesoporous channels of FSM-16, which were quite different from those of Pt nano-particles. (C) 1998 Elsevier Science B.V. All rights reserved.
  • T Yasuda, A Fukuoka, M Hirano, S Komiya
    CHEMISTRY LETTERS 1 29 - 30 1998年 [査読有り][通常論文]
     
    Reactions of a Pt-Mo heterodinuclear hydride complex, (dpe)HPt-MoCp(CO)(3) with alkynes at room temperature lead to facile reductive elimination giving HMoCp(CO)(3) accompanied by the formation of Pt(alkyne)(dpe). When terminal alkynes are employed, further Markovnikov addition of HMoCp(CO)(3) to the coordinated alkyne takes place to give new heterodinuclear alkenyl complexes (dpe)(mu-H2C=CR)Pt-MoCp(mu-CO)(CO).
  • M Hirano, M Akita, T Morikita, H Kubo, A Fukuoka, S Komiya
    JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS 19 3453 - 3458 1997年10月 [査読有り][通常論文]
     
    Reduction of [FeCl2(depe)(2)] (depe = Et2PCH2CH2PEt2) by sodium-naphthalene under nitrogen gave a dinitrogen complex of iron(o), [Fe(N-2)(depe)(2)] 1, in 72% yield. The crystal structure of 1 shows that the dinitrogen ligand bonds in an end-on fashion in a trigonal-bipyramidal geometry. Protonolysis of 1 by HCl gave trans-[FeH(Cl)(depe)(2)] with quantitative evolution of molecular nitrogen and then [FeCl2(depe)(2)] with molecular hydrogen. The dinitrogen ligand in 1 can be replaced by small molecules such as CO, CS2 or H-2 to give [Fe(CO)(depe)(2)], [Fe(CS2)(depe)(2)] and cis-[FeH2(depe)(2)] respectively. The molecular structure of [Fe(CO)(depe)(2)] has been established by X-ray analysis.
  • M Hirano, M Akita, T Morikita, H Kubo, A Fukuoka, S Komiya
    JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS 19 3453 - 3458 1997年10月 [査読有り][通常論文]
     
    Reduction of [FeCl2(depe)(2)] (depe = Et2PCH2CH2PEt2) by sodium-naphthalene under nitrogen gave a dinitrogen complex of iron(o), [Fe(N-2)(depe)(2)] 1, in 72% yield. The crystal structure of 1 shows that the dinitrogen ligand bonds in an end-on fashion in a trigonal-bipyramidal geometry. Protonolysis of 1 by HCl gave trans-[FeH(Cl)(depe)(2)] with quantitative evolution of molecular nitrogen and then [FeCl2(depe)(2)] with molecular hydrogen. The dinitrogen ligand in 1 can be replaced by small molecules such as CO, CS2 or H-2 to give [Fe(CO)(depe)(2)], [Fe(CS2)(depe)(2)] and cis-[FeH2(depe)(2)] respectively. The molecular structure of [Fe(CO)(depe)(2)] has been established by X-ray analysis.
  • M Hirano, M Akita, K Tani, K Kumagai, NC Kasuga, A Fukuoka, S Komiya
    ORGANOMETALLICS 16 19 4206 - 4213 1997年09月 [査読有り][通常論文]
     
    A CO2 complex of iron(0), Fe(CO2)(depe)(2) (I; depe = 1,2-bis(diethylphosphino)ethane) has been Prepared by replacement of N-2 in Fe(N-2)(depe)(2) by CO2. The X-ray structure analysis of 1 shows that it has a eta(2)(C,O)-CO2 ligand in a trigonal-bipyramidal Fe geometry with some contribution of an eta(1)(C) made. Reaction a I with R3SnCl in Et2O at -78 degrees C gives the iron carboxylate complexes FeCl(CO2SnR3)(depe)(2) (R = Me, (2a), Ph (2b)). The X-ray structure analysis of 2b shows that the CO2 fragment bridges between the Fe and Sn atoms in a mu-eta(1)(C):eta(2)(O,O')-CO2 fashion. Treatment of I with Me3SiCl results in the removal of an O atom from the CO2 ligand to give a cationic carbonyliron(II) complex, [FeCl(CO)(depe)(2)]Cl-+(-) (3a), and (Me3Si)(2)O. Similarly, 1 reacts with carbon electrophiles such as MeI and MeOTf to give the corresponding cationic iron(II) carbonyl complexes [FeX(CO)(depe)(2)]X-+(-) (X = I (3b), OTf (3c)) and Me2O.
  • M Hirano, M Akita, K Tani, K Kumagai, NC Kasuga, A Fukuoka, S Komiya
    ORGANOMETALLICS 16 19 4206 - 4213 1997年09月 [査読有り][通常論文]
     
    A CO2 complex of iron(0), Fe(CO2)(depe)(2) (I; depe = 1,2-bis(diethylphosphino)ethane) has been Prepared by replacement of N-2 in Fe(N-2)(depe)(2) by CO2. The X-ray structure analysis of 1 shows that it has a eta(2)(C,O)-CO2 ligand in a trigonal-bipyramidal Fe geometry with some contribution of an eta(1)(C) made. Reaction a I with R3SnCl in Et2O at -78 degrees C gives the iron carboxylate complexes FeCl(CO2SnR3)(depe)(2) (R = Me, (2a), Ph (2b)). The X-ray structure analysis of 2b shows that the CO2 fragment bridges between the Fe and Sn atoms in a mu-eta(1)(C):eta(2)(O,O')-CO2 fashion. Treatment of I with Me3SiCl results in the removal of an O atom from the CO2 ligand to give a cationic carbonyliron(II) complex, [FeCl(CO)(depe)(2)]Cl-+(-) (3a), and (Me3Si)(2)O. Similarly, 1 reacts with carbon electrophiles such as MeI and MeOTf to give the corresponding cationic iron(II) carbonyl complexes [FeX(CO)(depe)(2)]X-+(-) (X = I (3b), OTf (3c)) and Me2O.
  • Hirano M, Marumo T, Miyasaka T, Fukuoka A, Komiya S
    Chemistry Letters 4 297 - 298 1997年 [査読有り][通常論文]
     
    Selective ligand displacement of the cod ligand in Ru(cod)(cot) (1) [cod: 1,5-cyclooctadiene, cot: 1,3,5-cyclooctatriene] with trimethylphosphine gives fac-Ru(6-eta(1):1-3-eta(3)-C8H10)(PMe3)(3)(3) in benzene at 50 degrees C.
  • M Hirano, T Marumo, T Miyasaka, A Fukuoka, S Komiya
    CHEMISTRY LETTERS 4 297 - 298 1997年 [査読有り][通常論文]
     
    Selective ligand displacement of the cod ligand in Ru(cod)(cot) (1) [cod: 1,5-cyclooctadiene, cot: 1,3,5-cyclooctatriene] with trimethylphosphine gives fac-Ru(6-eta(1):1-3-eta(3)-C8H10)(PMe3)(3)(3) in benzene at 50 degrees C.
  • A Fukuoka, S Fukagawa, M Hirano, S Komiya
    CHEMISTRY LETTERS 4 377 - 378 1997年 [査読有り][通常論文]
     
    A palladium-containing heterodinuclear complex (dpe)MePd-Co(CO)(4) shows higher reactivity toward CO insertion than PdMeCl(dpe) and (dpe)MePt-Co(CO)(4) to give an acetyl complex (dpe)AcPd-Co(CO)(4). The insertion of CO ligand in Co(CO)(4) is a kinetically favorable process.
  • Y Usui, M Hirano, A Fukuoka, S Komiya
    CHEMISTRY LETTERS 10 981 - 982 1997年 [査読有り][通常論文]
     
    Gold(I) alkoxides, Au(OR)L (L = PPh3, PCy3; R = CH(CF3)(2), CH2CF3, Ph) smoothly abstract a hydrogen from transition metal hydrides (MI-I = CoH(CO)(4), MoHCp(CO)(3), WHCp(CO)(3), MnH(CO)(5), WHCp(CO)(2)(PPh3)) to give corresponding dinuclear complexes LAu-M with liberation of equimolar amount of ROH, Similar reactions of gold(III) alkoxides, cis-AuMe2-(OR)L also give dinuclear intermediates LMe2Au-M, from which preferential reductive elimination of ethane takes place when M is more electron withdrawing.
  • Fukuoka A, Sugiura T, Yasuda T, Taguchi T, Hirano M, Komiya S
    Chemistry Letters 4 329 - 330 1997年 [査読有り][通常論文]
     
    Novel heterodinuclear ethylplatinum complexes with a 1,2-bis(diphenylphosphino)ethane (dpe) ligand (dpe)EtPt-MLn (MLn = MoCp(CO)(3), WCp(CO)(3), Mn(CO)(5), Co(CO)(4)) have been synthesized and characterized. The dinuclear complexes show higher activity for B-H elimination reaction than a mononuclear PtEtCl(dpe), and in the case of Pt-Mo and Pt-W complexes the reaction proceeds with retention of the dinuclear structure.
  • A Fukuoka, T Sugiura, T Yasuda, T Taguchi, M Hirano, S Komiya
    CHEMISTRY LETTERS 4 329 - 330 1997年 [査読有り][通常論文]
     
    Novel heterodinuclear ethylplatinum complexes with a 1,2-bis(diphenylphosphino)ethane (dpe) ligand (dpe)EtPt-MLn (MLn = MoCp(CO)(3), WCp(CO)(3), Mn(CO)(5), Co(CO)(4)) have been synthesized and characterized. The dinuclear complexes show higher activity for B-H elimination reaction than a mononuclear PtEtCl(dpe), and in the case of Pt-Mo and Pt-W complexes the reaction proceeds with retention of the dinuclear structure.
  • A Fukuoka, Y Minami, N Nakajima, M Hirano, S Komiya
    JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL 107 1-3 323 - 328 1996年05月 [査読有り][通常論文]
     
    New organoplatinum-rhenium heterobimetallic complexes (organic ligand = Me (1), Et (2), CH(2)Ph (3), Ph (4)) with sulfur ligands have been prepared and characterized by IR, H-1 and C-13{H-1} NMR, elemental analysis, and chemical reactions. Complex 1 was thermally more stable than related PtMeCl(cod) (5) and PtMe(SPh)(cod) (6). On the other hand, thermolysis reaction of 2 in diphenylmethane at 80 degrees C afforded ethylene in a larger yield than those for PtEtCl(cod) (7) and PtEt(SPh)(cod) (8). From the estimation of electronegativity using H-1 NMR data, it was suggested that Pt in 2 was more electron deficient than in 7 and 8. It is thus proposed that SRe(CO)(4) units in 2 decreases the electron density at Pt, resulting in the promotion of apparent beta-H elimination to form ethylene.
  • Sanshiro Komiya, Takuo Sone, Yoko Usui, Masafumi Hirano, Atsushi Fukuoka
    Gold Bulletin 29 4 131 - 136 1996年 [査読有り][通常論文]
     
    Condensation reactions between active methylene compounds, CH 2(X)(Y), such as alkyl cyanoacetate or acetophenone and benzaldehyde proceed smoothly in the presence of catalytic amounts of gold alkoxides, Au(OR)L (L = PPh3: R = CH2CF3 (1a), CH(CF 3)2 (1b) L = PCy3: R = CH2CF 3 (1c), CH(CF3)2 (1d) or AuMe2(OR)L (L = PPh3: R = CH2CF3 (2a), CH(CF 3)2 (2b). Gold(I) complexes show higher catalytic activity than gold(III). In the catalytic system, the catalysts exist as the C-bonded gold enolate complexes Au(I)(CH(X)(Y))(L) or Au(III)Me2(CH(X)(Y))(L), which can be isolated independently from the reactions of gold alkoxides with the corresponding active methylene compounds. The catalytic activity of the gold alkoxides is generally higher than that of isolated C-bonded gold enolates. The reaction rate increases with increase in the concentrations of catalyst and benzaldehyde, but is independent of the concentration of alkyl cyanoacetate. A reaction mechanism involving two catalytic pathways has been proposed.
  • Fukuoka A
    Petrotech 19 3 13 - 17 1996年 [査読有り][通常論文]
  • SI Murahashi, T Naota, H Taki, M Mizuno, H Takaya, S Komiya, Y Mizuho, N Oyasato, M Hiraoka, M Hirano, A Fukuoka
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 117 50 12436 - 12451 1995年12月 [査読有り][通常論文]
     
    The ruthenium(II)-catalyzed reaction of nitriles with carbonyl compounds proceeds highly efficiently under neutral and mild conditions to give alpha,beta-unsaturated nitriles. Under similar reaction conditions, nitriles react with olefins bearing electron-withdrawing groups to give the corresponding Michael adducts. The efficiency of the reaction is illustrated by the selective additions to alpha,beta-unsaturated aldehydes and acetylenes bearing electron-withdrawing groups, which are difficult to perform using conventional bases. Chemoselective aldol and Michael reactions of nitriles can be performed in the presence of other active methylene compounds. Tandem Michael and Michael-aldol condensations of nitriles 30 can be performed with high diastereoselectivity. These reactions can be rationalized by assuming oxidative addition of ruthenium(0) to the alpha=C-H bond of nitriles and subsequent insertions to carbonyl compounds or olefins. As the key intermediates and active catalysts hydrido(N-bonded enolato)ruthenium(II) complexes, mer-RuH(NCCHCO(2)R)(NCCH(2)CO(2)R)(PPh(3))(3) (R = Me (41a), Et (41b), n-Bu (41c) have been upon treatment of RuH2(PPh(3))(4) (3) or RuH(C2H4)(PPh(3))(2)(PPh(2)C(6)H(4)) (4) with alkyl cyanoacetates. Kinetic study of the catalytic aldol reaction of ethyl cyanoacetate with benzaldehyde indicates that the rate-determining step reaction of enolato complex 41 with aldehydes.
  • A FUKUOKA, N GOTOH, N KOBAYASHI, M HIRANO, S KOMIYA
    CHEMISTRY LETTERS 7 567 - 568 1995年07月 [査読有り][通常論文]
     
    Carboxylic acids RCOOH (R = Me, Et, Ph) are catalytically produced from carbon dioxide, dihydrogen, and the corresponding organic iodides in the presence of homogeneous Ru/Co or Ni/Co bimetallic catalysts.
  • T SONE, S OZAKI, NC KASUGA, A FUKUOKA, S KOMIYA
    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 68 6 1523 - 1533 1995年 [査読有り][通常論文]
     
    cis-Dimethyl(eta(1)-allyl)(triphenylphosphine)gold(III), cis-[AuMe(2)(eta(1)-allyl)(PPh(3))] (eta(1)-allyl=allyl (1), crotyl (2), methallyl (3)) has been synthesized by reaction of cis-[AuMe(2)X(PPh(3))] (X=I, NO3) with corresponding Grignard reagents. X-Ray structure analysis of 2 shows that 2 has a typical square planar cis configuration and the crotyl ligand binds to Au by eta(1)-mode: orthorhombic, space group P2(1)2(1)2(1), a=9.816(2), b=23.208(4), c=9.5290(9) Angstrom, Z=4, R(R(w))=0.037(0.041) with use of 2551 reflections. Reactions of 2 with HCl and Br-2 selectively give 1-butene and 3-bromo-1-butene, respectively, indicating gamma-regioselectivity of the reactions. Compounds 1-3 react with aldehydes and ketones to give the corresponding homoallyl alcohols. C-C bond formation also takes place at the gamma-position of eta(1)-allyl moiety selectively. The rate of the allylation reaction of carbonyl compounds decreases in the order of methallyl (3)> allyl (1) >crotyl (2) gold(III) complexes. The homoallyl alcohol formed by the reaction of 2 with benzaldehyde is a diastereoisomeric mixture of 5-methyl-1-phenyl-3-buten-1-ol, with high anti selectivity. Both the reaction rate and anti selectivity in the allylation reaction were reduced by addition of tertiary phosphines such as PPh(3) and PCy(3), and a 6-membered transition state has been proposed, which indicates coordination of the carbonyl group to a T-shape Au intermediate produced by dissociation of the PPh(3) ligand.
  • A FUKUOKA, T SADASHIMA, ENDO, I, N OHASHI, Y KAMBARA, T SUGIURA, K MIKI, N KASAI, S KOMIYA
    ORGANOMETALLICS 13 10 4033 - 4044 1994年10月 [査読有り][通常論文]
     
    A series of heterodinuclear platinum - tungsten and - molybdenum complexes (cod)RPt-M(CP)(CO)3 has been prepared by the metathetical reactions: M = W, Cp = Cp, R = Me (1a), Et (1b), Ph (1c), 2-MeC6H4 (1d), 4-MeC6H4 (1e), 2,6-(Me)2C6H3 (1f), 4-MeOC6H4 (1g), C6F5 (1h), 4-FC6H4 (1i), 4-ClC6H4 (1j); M = W, CP = C5H4Me, R = Me (2a), Ph (2b), M = W, Cp = C5H4COOMe, R = Me (3a), Ph (3b); M = Mo, CP = Cp, R = Me (4a), Ph (4b), 2-MeC6H4 (4c). (cod)PhPt-MoCp(CO)3 (4b) crystallizes in the monoclinic system in space group P2(1)/n with a = 14.291(5) angstrom, b = 12.738(3) angstrom, c = 11.988(4) angstrom, beta = 112.01(3)-degrees, Z = 4, R = 0.057 (R(w) = 0.078), based on 3719 reflections with \F(o)\ > 3sigma(\F(o)\. 4b is isostructural to the Pt-W analogue 1c determined previously and the geometry at Pt is square planar, where the Pt-Mo bond distance is 2.832(1) angstrom. The alkyl and aryl ligands on Pt migrate to the other metal in thermolysis in C6D6 at 70-degrees-C. The migration is accelerated by CO as well as by PPh3 or P(OPh)3. In contrast, the reaction of 1a with PMe3 does not result in the methyl migration but affords [PtMe(PMe3)3]+ [WCp(CO)3]- (5). Moreover, the migration is accelerated by acrylonitrile and the rate is first order in the concentration of acrylonitrile, but further addition of COD retards the rate of migration. From kinetic investigation, the mechanism of the methyl migration for 1a is proposed. In the mechanism, acrylonitrile coordinates to 1a to form a five-coordinated intermediate (6), and 6 dissociates COD to form a three-coordinated intermediate (7). MeWCp(CO)3 (8) is produced from 1a, 6, and 7.
  • A FUKUOKA, T SADASHIMA, ENDO, I, N OHASHI, Y KAMBARA, T SUGIURA, K MIKI, N KASAI, S KOMIYA
    ORGANOMETALLICS 13 10 4033 - 4044 1994年10月 [査読有り][通常論文]
     
    A series of heterodinuclear platinum - tungsten and - molybdenum complexes (cod)RPt-M(CP)(CO)3 has been prepared by the metathetical reactions: M = W, Cp = Cp, R = Me (1a), Et (1b), Ph (1c), 2-MeC6H4 (1d), 4-MeC6H4 (1e), 2,6-(Me)2C6H3 (1f), 4-MeOC6H4 (1g), C6F5 (1h), 4-FC6H4 (1i), 4-ClC6H4 (1j); M = W, CP = C5H4Me, R = Me (2a), Ph (2b), M = W, Cp = C5H4COOMe, R = Me (3a), Ph (3b); M = Mo, CP = Cp, R = Me (4a), Ph (4b), 2-MeC6H4 (4c). (cod)PhPt-MoCp(CO)3 (4b) crystallizes in the monoclinic system in space group P2(1)/n with a = 14.291(5) angstrom, b = 12.738(3) angstrom, c = 11.988(4) angstrom, beta = 112.01(3)-degrees, Z = 4, R = 0.057 (R(w) = 0.078), based on 3719 reflections with \F(o)\ > 3sigma(\F(o)\. 4b is isostructural to the Pt-W analogue 1c determined previously and the geometry at Pt is square planar, where the Pt-Mo bond distance is 2.832(1) angstrom. The alkyl and aryl ligands on Pt migrate to the other metal in thermolysis in C6D6 at 70-degrees-C. The migration is accelerated by CO as well as by PPh3 or P(OPh)3. In contrast, the reaction of 1a with PMe3 does not result in the methyl migration but affords [PtMe(PMe3)3]+ [WCp(CO)3]- (5). Moreover, the migration is accelerated by acrylonitrile and the rate is first order in the concentration of acrylonitrile, but further addition of COD retards the rate of migration. From kinetic investigation, the mechanism of the methyl migration for 1a is proposed. In the mechanism, acrylonitrile coordinates to 1a to form a five-coordinated intermediate (6), and 6 dissociates COD to form a three-coordinated intermediate (7). MeWCp(CO)3 (8) is produced from 1a, 6, and 7.
  • A FUKUOKA, A SATO, Y MIZUHO, M HIRANO, S KOMIYA
    CHEMISTRY LETTERS 9 1641 - 1644 1994年09月 [査読有り][通常論文]
     
    Novel mono- and dinuclear organo(siloxo)platinum complexes PtR(OSiPh(3))(cod) (R = Me, Ph) and [{PtMe(cod)O}Ph(2)Si]O-2 have been prepared and characterized. The molecular structure of PtPh(OSiPh(3))(cod) has been determined by X-ray structure analysis. The activity for reduction of PtMe(OSiPh(3))(cod) and PtMe(OPh)(cod) by H-2 is higher than that of PtMe(2)(cod).
  • A FUKUOKA, T SADASHIMA, T SUGIURA, XS WU, Y MIZUHO, S KOMIYA
    JOURNAL OF ORGANOMETALLIC CHEMISTRY 473 1-2 139 - 147 1994年06月 [査読有り][通常論文]
     
    New Platinum-containing heterodinuclear complexes with methyl and 1,2-bis(diphenylphosphino)ethane (dpe) ligands have been prepared by metathetical reactions of PtMe(NO3)(dpe) with Na[ML(n)]: ML(n) = MoCp(CO)3 (1); WCp(CO)3 (2); Mn(CO)5 (3); FeCp(CO)2 (4); Co(CO)4 (5). The molecular structure of (dpe)MePt-FeCP(CO)2 . THF (4 . THF) has been determined by X-ray crystallography: the geometry at Pt is square planar and the FeCP(CO)2 moiety has a piano-stool type structure. Thermolysis of 4 in C6D6 at 70-degrees-C for 2 h gives MeFeCp(CO)2 (8) in 30% yield, but other dinuclear complexes are thermally stable under these conditions. Methyl migration to produce 8 was accelerated by the addition of electron-deficient olefins such as acrylonitrile and fumaronitrile. From the kinetic study, a mechanism involving two pathways is proposed: one is direct thermolysis from 4 to 8, while the other is the associative reductive elimination of 8 from the olefin-coordinated intermediate 9.
  • S KOMIYA, M AKITA, N KASUGA, M HIRANO, A FUKUOKA
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS 9 1115 - 1116 1994年05月 [査読有り][通常論文]
     
    Reaction of [Fe(N-2)(depe)(2)] with carbon dioxide gives trigonal bipyramidal [Fe(eta(2)-CO2)(depe)(2)], where the coordinated CO2 lies on equatorial plane by an eta(2)-fashion and converts into dimethyl ether and [FeX(CO)(depe)(2)]X (X = I, OTf) on interaction with methyl halide or triflate.
  • S KOMIYA, M AKITA, N KASUGA, M HIRANO, A FUKUOKA
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS 9 1115 - 1116 1994年05月 [査読有り][通常論文]
     
    Reaction of [Fe(N-2)(depe)(2)] with carbon dioxide gives trigonal bipyramidal [Fe(eta(2)-CO2)(depe)(2)], where the coordinated CO2 lies on equatorial plane by an eta(2)-fashion and converts into dimethyl ether and [FeX(CO)(depe)(2)]X (X = I, OTf) on interaction with methyl halide or triflate.
  • S KOMIYA, T KABASAWA, K YAMASHITA, M HIRANO, A FUKUOKA
    JOURNAL OF ORGANOMETALLIC CHEMISTRY 471 1-2 C6 - C7 1994年05月 [査読有り][通常論文]
     
    (Pi-allyl)(trifluoroacetato)tris(triethylphosphine)ruthenium(II) has been isolated by oxidative addition of allyl trifluoroacetate to Ru(cod)(cot) in the presence of triethylphosphine ligand.
  • S KOMIYA, H AWATA, S ISHIMATSU, A FUKUOKA
    INORGANICA CHIMICA ACTA 217 1-2 201 - 202 1994年03月 [査読有り][通常論文]
     
    Water-soluble (tri(hydroxymethyl)phosphine)gold(I) complexes containing a nucleoside ligand, [Au(Nuc){P(CH2OH)3}]+NO3- (Nuc=Guo, Ado, Cyd) have been synthesized by the reaction of AuCl(P(CH2OH)3 with the corresponding nucleoside in the presence of silver nitrate in ethanol at room temperature.
  • M ICHIKAWA, T SHIDO, FS XIAO, A FUKUOKA
    NATURAL GAS CONVERSION II 81 C 367 - 372 1994年 [査読有り][通常論文]
     
    The bimetallic RuM(M=Co, Fe, Mo, Ni, Rh, Cr, Mn) catalysts were prepared from SiO2-supported carbonyl clusters, and it was found that the RuCo, RuFe and RuMo bimetallic cluster-derived catalysts showed higher activity and selectivity for oxygenates such as C-1-C-5 alcohols in CO hydrogenation(CO/H-2=0.5-1.0, 5 bar, 519K). In contrast, hydrocarbons and CO2 were preferentially obtained on the catalysts prepared from SiO2-supported Ru6C, Ru-3 and Co-4 carbonyl clusters. The RuNi, RuMn and RuRh catalysts provided poor selectivities for oxygenates. The promotion toward alcohol formation on RuCo, RuFe and RuMo cluster-derived catalysts was proposed to be associated the adjacent Ru-M(d+) (M=Co, Fe, Mo) at the cluster-oxide support interface, which has been characterized by means of the XPS spectroscopy. In situ FT-IR studies revealed that the bands centered at 1584 cm(-1), possibly assigned to a eta(2)-formyl intermediate on the RuM (M=Co, Fe, Mo) bimetal catalysts have a good relationship with the rates of higher alcohol formation in CO hydrogenation.
  • M HIRANO, M HIRAI, Y ITO, A FUKUOKA, S KOMIYA
    CHEMISTRY LETTERS 1 165 - 166 1994年01月 [査読有り][通常論文]
     
    Rhenium(I) enolate complexes Re(NCCHCO2Et)[NC(EtO2C)C=CHPh](PMe2Ph)4 and Re(NCCHCO2Et)(NCCH2CO2Et)(PMe2Ph)4 are found to catalyze unique olefin metathesis reaction of tetracyanoethylene with ethyl alpha-cyanocinnamate to give 1,1-dicyano-2-phenylethylene and ethyl 2,3,3-tricyanopropenoate at room temperature.
  • M HIRANO, Y ITO, M HIRAI, A FUKUOKA, S KOMIYA
    CHEMISTRY LETTERS 12 2057 - 2060 1993年12月 [査読有り][通常論文]
     
    Rhenium(I) dinitrogen complex cis-ReH(N2)(PMe2Ph)4 catalyzes an aldol type reaction of ethyl cyanoacetate with benzaldehyde under moderate conditions. Rhenium enolate complexes Re(NCCRCO2R')(NCCHRCO2R')(PMe2Ph)4 (R = H, R' = Me; R = H, R' = Et; R = H, R' = n-Bu; R = Me, R' = Et) and Re(NCCHCO2Et)-[NC(EtO2C)C=CHPh](PMe2Ph)4 as active intermediates of the aldol type reactions have been isolated.
  • S KOMIYA, M AKITA, A YOZA, N KASUGA, A FUKUOKA, Y KAI
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS 9 787 - 788 1993年05月 [査読有り][通常論文]
     
    A zerovalent iron dinitrogen complex [Fe(N2)(depe)2] having 1,2-bis(diethylphosphino)ethane ligands has been prepared by reduction of [FeCl2(depe)2] with sodium-naphthalene in tetrahydrofuran under nitrogen at room temperature.
  • S KOMIYA, M AKITA, A YOZA, N KASUGA, A FUKUOKA, Y KAI
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS 9 787 - 788 1993年05月 [査読有り][通常論文]
     
    A zerovalent iron dinitrogen complex [Fe(N2)(depe)2] having 1,2-bis(diethylphosphino)ethane ligands has been prepared by reduction of [FeCl2(depe)2] with sodium-naphthalene in tetrahydrofuran under nitrogen at room temperature.
  • S KOMIYA, K NAKADA, M HIRATA, A FUKUOKA
    CHEMISTRY LETTERS 3 457 - 460 1993年03月 [査読有り][通常論文]
     
    Reactions of nitrato(triarylphosphine)gold(I) complexes [Au(PR3)(NO3)] with nucleosides such as guanosine (Guo), adenosine (Ado), and cytidine (Cyd) give new nucleoside-containing gold(I) complexes, [Au(PR3)(Nuc)](NO3) (R = Ph, o-anisyl, p-anisyl; Nuc = Guo, Ado, Cyd) in DMSO-d6. NMR study reveals that the coordinated Guo ligand rapidly exchanges with free Guo by an associative mechanism.
  • M ICHIKAWA, Q ZHUANG, GJ LI, K TANAKA, T FUJIMOTO, A FUKUOKA, AA TSYGANENKO, JC MOL, W GRUNERT, WK HALL, JC CONESA, DC KONINGSBERGER, J VEDRINE, JJ ROONEY
    NEW FRONTIERS IN CATALYSIS, PTS A-C 75 529 - 541 1993年 [査読有り][通常論文]
  • GJ LI, T FUJIMOTO, A FUKUOKA, M ICHIKAWA
    NEW FRONTIERS IN CATALYSIS, PT B 75 1607 - 1610 1993年 [査読有り][通常論文]
  • T FUJIMOTO, A FUKUOKA, S IIJIMA, M ICHIKAWA
    JOURNAL OF PHYSICAL CHEMISTRY 97 2 279 - 281 1993年01月 [査読有り][通常論文]
     
    The platinum carbonyl cluster [Pt12(CO)24]2- dissolved in tetrahydrofuran was transformed into [Pt9(CO)18]2-by laser irradiation (532 nm), as monitored by infrared spectroscopy. Further laser irradiation resulted in the formation of a brown product whose infrared spectrum was different from those of known platinum carbonyl clusters. From observations by scanning tunneling microscopy (STM) and high-resolution transmission electron microscopy (HRTEM), the product is suggested to be a new high-nuclearity platinum carbonyl of size ca. 2.0 nm.
  • M ICHIKAWA, Q ZHUANG, GJ LI, K TANAKA, T FUJIMOTO, A FUKUOKA, AA TSYGANENKO, JC MOL, W GRUNERT, WK HALL, JC CONESA, DC KONINGSBERGER, J VEDRINE, JJ ROONEY
    STUDIES IN SURFACE SCIENCE AND CATALYSIS 75 C 529 - 541 1993年 [査読有り][通常論文]
     
    SiO2-grafted dinuclear molybdenum species was prepared from Mo2(OAc)4/SiO2. It was demonstrated by ESR, UV-vis, FTIR, XANES and EXAFS spectroscopic studies that Mo2(OAc)4 reacts with silanol on SiO2 by thermal activation at 350-degrees-C, resulting in uniform formation of a ESR active [Mo=Mo]V (g=1.928, R(Mo-Mo)=2.11angstrom, C.N.=0.6). It was found that the resulting dinuclear Mo species is selective and highly active for propene metathesis at 20-degrees-C, whereas inactive for ethene homologation. The excess thermal treatment at above 400-degrees-C causes the complete cleavage of Mo-Mo bond of the grafted Mo-dimer species to give a highly dispersed Mo5+ oxide, which is negligibly active for propene metathesis, but relatively active for ethene homologation. In contrast, the catalysts prepared from Mo2(OAc)4 impregnated on Al2O3 ana inside NaY zeolite are not active for propene metathesis.
  • GJ LI, T FUJIMOTO, A FUKUOKA, M ICHIKAWA
    STUDIES IN SURFACE SCIENCE AND CATALYSIS 75 C 1607 - 1610 1993年 [査読有り][通常論文]
     
    [Pt9(CO)18]2-/NaY(orange-brown, 2056 and 1798cm-1), and [Pt12(CO)24]2-/NaY(dark-green, 2080 and 1824cm-1) were stoichiometrically synthesized by the reductive carbonylation at 323-373K of [Pt(NH3)4]2+/NaY, and Pt2+/NaY respectively. TPD and TPR studies reveal that Pt9 and Pt12 carbonyl clusters are considerably stabilized inside NaY cavities, rather than the external complexes. Pt-L3-edge EXAFS measurement demonstrated that they are consisted with the Pt carbonyl clusters having trigonal prismatic Pt9 and Pt12 frameworks inferred to [NEt4]2 [Pt3(CO)6]n (n=3,4). The intrazeolite Pt9 and Pt12 carbonyl clusters exhibited higher catalytic activity in NO reduction by CO towards N2 and N2O at 473K, compared with those on the conventional Pt/Al2O3 catalysts. Removal of carbonyls with mild oxidation, and H-2-reduction of zeolite-included Pt9 and Pt12 carbonyl clusters provide the dispersed Pt particles which chemistorb CO and H-2 in the storichiometriy of CO/Pt =1.83 and H/Pt=1.26.
  • FS XIAO, A FUKUOKA, M ICHIKAWA
    JOURNAL OF CATALYSIS 138 1 206 - 222 1992年11月 [査読有り][通常論文]
  • S KOMIYA, M IWATA, T SONE, A FUKUOKA
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS 16 1109 - 1110 1992年08月 [査読有り][通常論文]
     
    Alkoxogold(I) complexes having a tertiary phosphine ligand, Au(OR)L [R = CH2CF3, CH(CF3)2; L = PPh3, PCy3] have been synthesized by the metathetical reactions of chloro(tertiary phosphine)gold(I) and potassium fluorinated alkoxides in tetrahydrofuran at room temperature.
  • S KOMIYA, M IWATA, T SONE, A FUKUOKA
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS 16 1109 - 1110 1992年08月 [査読有り][通常論文]
     
    Alkoxogold(I) complexes having a tertiary phosphine ligand, Au(OR)L [R = CH2CF3, CH(CF3)2; L = PPh3, PCy3] have been synthesized by the metathetical reactions of chloro(tertiary phosphine)gold(I) and potassium fluorinated alkoxides in tetrahydrofuran at room temperature.
  • N TAKAHASHI, T TAKEYAMA, T FUJIMOTO, A FUKUOKA, M ICHIKAWA
    CHEMISTRY LETTERS 8 1441 - 1444 1992年08月 [査読有り][通常論文]
     
    The results obtained by EXAFS and TPD of CO techniques clearly showed that Rh6(CO)16 is formed by the exposure of partially reduced Rh/active carbon to CO at 353 K, and further converted into metallic rhodium particles at 473 K.
  • FS XIAO, A FUKUOKA, M ICHIKAWA, W HENDERSON, DF SHRIVER
    JOURNAL OF MOLECULAR CATALYSIS 74 1-3 379 - 390 1992年07月 [査読有り][通常論文]
     
    The bimetallic RuCo3, RuCo2 and Ru3MxC (M=Co, Fe, Ni, Mo, Rh, Cr, Mn, x=1-3) catalysts were prepared from SiO2-supported carbonyl clusters, and it was found that the RuCo, RuFe and RuMo bimetallic carbonyl cluster-derived catalysts showed higher activity and selectivity, for oxygenates such as C1-C5 alcohols in CO hydrogenation. In contrast, hydrocarbons and CO2 were preferentially obtained on the catalysts prepared from SiO2-supported homometallic Ru6C, Ru3 and Co, carbonyl clusters. The RuNi, RuCr, RuMn and RuRh carbonyl cluster-derived catalysts provided poor activity and selectivity for oxygenates. The promotion toward alcohol formation on RuCo, RuFe and RuMo cluster-derived catalysts was proposed to be associated with the adjacent Ru-M(delta+) (M=Co, Fe, and Mo) at the cluster-oxide support interface to offer C- and O-ended CO (nu(CO) = 1680 cm-1). In situ FT-IR studies revealed that the band at 1584 cm-1, possibly assigned to a formyl intermediate on RuM (M=Co, Fe, and Mo) bimetallic cluster-derived at 453 K under syngas (CO/H-2=0.5), has a good linear relationship with the rate of oxygenate formation, whereas the 1584 cm-1 band was not observed on RuMn, RuCr, RuRh and RuNi bimetallic and homometallic cluster-derived catalysts showing poor activity for oxygenates. At higher temperatures the higher alcohols (C2-C5) are produced via CO dissociation and acetyl intermediate (nu(CO) = 1555 cm-1) formation from CO + H-2 on the RuCo cluster-derived catalysts.
  • FS XIAO, A FUKUOKA, M ICHIKAWA, W HENDERSON, DF SHRIVER
    REACTION KINETICS AND CATALYSIS LETTERS 47 2 149 - 158 1992年07月 [査読有り][通常論文]
     
    The ruthenium catalyst prepared from triruthenium ketenylidene cluster exhibited high catalytic activity in CO hydrogenation, compared with the catalyst from [HRu3(CO)11]-. The high activity possibly resulted from the ketenyl group (CCO) that could be partly converted to carbide species.
  • T FUJIMOTO, A FUKUOKA, M ICHIKAWA
    CHEMISTRY OF MATERIALS 4 1 104 - 107 1992年01月 [査読有り][通常論文]
     
    Scanning tunneling microscopy (STM) images were obtained from an isolated aggregate of Pt carbonyl clusters [NEt4]2[Pt12(CO)24], which were adsorbed from the tetrahydrofuran solution onto the surface of a freshly cleaved HOPG (highly oriented pyrolytic graphite) under the nitrogen atmosphere. The in situ STM images demonstrated the morphological changes of the surface-bound Pt12 carbonyl clusters under the pulse laser irradiation (532 nm; 2-3 mJ), resulting in the effective decarbonylation and fragmentation which was implied by the diffuse reflectance FTIR, coupled with mass. The Pt12 carbonyl clusters were converted by the successive pulse laser activation into a highly dispersed Pt microcrystalline (18 x 50 angstrom2), which was imaged by STM.
  • GJ LI, T FUJIMOTO, A FUKUOKA, M ICHIKAWA
    CATALYSIS LETTERS 12 1-3 171 - 186 1992年 [査読有り][通常論文]
     
    [Pt9(CO)18]2-/NaY (orange-brown, 2056 and 1798 cm-1), [Pt12(CO)24]2-/NaY (dark-green, 2080 and 1824 cm-1 and [Pt15(CO)30]2-/NaX (yellow-green, 2100 and 1865 cm-1) were stoichiometrically synthesized by the reductive carbonylation of [Pt(NH3)4]2+/NaY, Pt2+/NaY and Pt2+/NaX, respectively. The IR bands characteristic of their linear carbonyls shift to higher frequencies whereas the bridging CO bands to lower frequencies, compared with those on the external zeolites and in solution. In-situ FTIR studies suggested that the subcarbonyl species such as PtO(CO) and "Pt3(CO)3(mu-2 - CO)3" are formed as the proposed intermediates towards [Pt12(CO)24]2-/NaY in the reductive carbonylation of Pt2+/NaY. (CO)-C-13 exchange reaction preceded with the different intrazeolite Pt carbonyl species in the following order of activity at 298-343 K: "Pt3(CO)3(mu-2 - CO)3"/NaY >> PtO(CO)/NaY > [Pt9(CO)18]2-/NaY > [Pt12(CO)24]2-/NaY. Pt-L3-edge EXAFS measurement for these synthesized samples demonstrated that they are consistent with the Pt carbonyl clusters having trigonal prismatic Pt9 and Pt12 frameworks inferred to a series of the Chini complexes such as [NEt4]2[Pt3(CO)6]n (n = 3-5). The intrazeolite Pt9 and Pt12 carbonyl clusters exhibited higher catalytic activity in NO reduction by CO towards N2 and N2O at 473 K, compared with those on the conventional Pt/Al2O3 catalysts. The mechanism of intrazeolite Pt9-Pt15 carbonyl cluster formation are discussed in terms of the intrazeolite basicity and acidity.
  • A FUKUOKA, N OHASHI, S KOMIYA
    CHEMISTRY LETTERS 1 69 - 72 1992年01月 [査読有り][通常論文]
     
    New styryl ruthenium-molybdenum and -tungsten complexes Cp(CO)3M-Ru (trans-styryl)(CO)(PPh3)2 [M = Mo (2), W (3)] have been prepared by the metathetical reactions of Ru(trans-styryl)Cl(CO)(PPh3)2 with Na[MCp(CO)3]. The reactions of 2 with CO and with PMe3 give Cp(CO)3Mo-Ru(trans-styryl)(CO)2(PPh3)2 (4) and Cp(CO)3Mo-Ru(trans-styryl)(CO)(PMe3)2 (5), respectively. The complexes of 2, 3, 4, and 5 have been characterized by IR, H-1 NMR, P-31{H-1} NMR spectroscopy, and elemental analysis.
  • GJ LI, T FUJIMOTO, A FUKUOKA, M ICHIKAWA
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS 19 1337 - 1339 1991年10月 [査読有り][通常論文]
     
    The NaY zeolite-entrapped clusters [Pt3(CO)6]n2- (n = 3, 4), synthesized by a ship-in-bottle technique, were characterized by Pt-L edge EXAFS (extended X-ray absorption fine structure), Fourier transform IR and UV-VIS spectroscopy, and exhibited high catalytic activity in NO reduction by CO to give N2 and N2O at 300-473 K.
  • GJ LI, T FUJIMOTO, A FUKUOKA, M ICHIKAWA
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS 19 1337 - 1339 1991年10月 [査読有り][通常論文]
     
    The NaY zeolite-entrapped clusters [Pt3(CO)6]n2- (n = 3, 4), synthesized by a ship-in-bottle technique, were characterized by Pt-L edge EXAFS (extended X-ray absorption fine structure), Fourier transform IR and UV-VIS spectroscopy, and exhibited high catalytic activity in NO reduction by CO to give N2 and N2O at 300-473 K.
  • A TRUNSCHKE, H EWALD, H MIESSNER, A FUKUOKA, M ICHIKAWA, HC BOTTCHER
    MATERIALS CHEMISTRY AND PHYSICS 29 1-4 503 - 508 1991年09月 [査読有り][通常論文]
     
    Molybdenum-promoted Rh/SiO2 catalysts have been prepared from rhodium and molybdenum salts and from a heteronuclear Rh-Mo cluster as precursors. These catalysts have been compared with unpromoted Rh/SiO2 in CO hydrogenation and in ethene hydroformylation reactions. Mo promotes the CO hydrogenation both on salt- and cluster-derived catalysts, but the product distribution is different with a significantly enhanced selectivity to oxygenated products on cluster-derived samples. To test the CO insertion capability of the catalysts, ethene hydroformylation was performed under mild conditions (393 K-473 K, 0.1 MPa) and at CO hydrogenation conditions (473 K-573 K, 1 MPa). Only with the conditions of CO hydrogenation was it possible to show that the higher selectivity of the cluster-derived catalyst towards alcohols in the CO hydrogenation is due to the higher CO insertion capability of the cluster-derived catalyst.
  • K MACHIDA, A FUKUOKA, M ICHIKAWA, M ENYO
    JOURNAL OF THE ELECTROCHEMICAL SOCIETY 138 7 1958 - 1965 1991年07月 [査読有り][通常論文]
     
    Platinum and platinum-based bimetallic carbonyl cluster complex anions, [Pt3n(CO)6n]2- (n = 3, 5), [Pt3Fe3(CO)15]2-, [PtCl2(SnCl3)2]2- and [Pt3Sn8Cl20]4-, were introduced by an ion exchange technique on graphite disks, treated beforehand with an organosilane reagent of quarternary ammonium chloride, or on anion exchange membranes to prepare metal cluster-attached electrodes. The Auger electron spectra showed that platinum species were indeed attached on the electrodes. Except for the Pt-Sn electrodes, the redox voltammograms due to H+/H(a) in the potential range 0.05-0.40 V (RHE) were clearly observed in 0.5M H2SO4 solution, which are very similar as those observed on Pt electrodes-prepared by vacuum evaporation. Dependence of the electrocatalytic activity for the anodic oxidation of methanol on the cluster size indicated that the activity becomes significant on electrodes with the precursor unit size of above Pt9. Particularly, the Pt-15-derived electrodes, following by heating in H-2 or air at 373-573 K, were found to be highly active for the anodic oxidation of methanol.
  • Q ZHUANG, A FUKUOKA, T FUJIMOTO, K TANAKA, M ICHIKAWA
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS 11 745 - 746 1991年06月 [査読有り][通常論文]
     
    SiO2-grafted dinuclear molybdenum species derived from Mo2(OAc)4, e.g. [Mo = Mo]v, which are characterized by ESR and EXAFS spectroscopy, exhibit marked catalytic activity for propene metathesis reaction, but are inactive for ethene homologation.
  • Q ZHUANG, A FUKUOKA, T FUJIMOTO, K TANAKA, M ICHIKAWA
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS 11 745 - 746 1991年06月 [査読有り][通常論文]
     
    SiO2-grafted dinuclear molybdenum species derived from Mo2(OAc)4, e.g. [Mo = Mo]v, which are characterized by ESR and EXAFS spectroscopy, exhibit marked catalytic activity for propene metathesis reaction, but are inactive for ethene homologation.
  • M ICHIKAWA, T KIMURA, A FUKUOKA
    CHEMISTRY OF MICROPOROUS CRYSTALS 60 C 335 - 342 1991年 [査読有り][通常論文]
  • M ICHIKAWA, FS XIAO, CG MAGPANTY, A FUKUOKA, W HENDERSON, DF SHRIVER
    NATURAL GAS CONVERSION 61 C 297 - 303 1991年 [査読有り][通常論文]
  • A TRUNSCHKE, HC BOTTCHER, A FUKUOKA, M ICHIKAWA, H MIESSNER
    CATALYSIS LETTERS 8 2-4 221 - 228 1991年 [査読有り][通常論文]
     
    Molybdenum promoted Rh/SiO2 catalysts have been prepared by using the heteronuclear cluster (C5H5)3RhMo2(CO)5 as well as metal salt precursors. The promoting effect of molybdenum has been studied for the hydroformylation of ethene and propene and the hydrogenation of acetaldehyde. It has been found that molybdenum, especially on the cluster-derived catalyst, increases both the hydrogenation and the hydroformylation rate of the olefins. No specific influence on the CO insertion reaction could be obtained. As an explanation, the promotion of the inital step to form intermediate surface alkyl groups has been proposed as the rate determining step for ethene hydroformylation. The promotion of the alcohol formation by bimetallic centers having Rh and Mo in close vicinity has been supported by the results of the hydrogenation of acetaldehyde.
  • T YAMADA, Y KURODA, A FUKUOKA, M ICHIKAWA, K TANAKA
    JOURNAL OF ELECTRON SPECTROSCOPY AND RELATED PHENOMENA 54 C 845 - 854 1990年12月 [査読有り][通常論文]
     
    The surface reaction of the adsorbed hydroxyl group OH(a) with Rh(CO)2(pi-C3H5) delivered from the gas phase: OH(a) + Rh(CO)2(pi-C3H5)(g)-->O-Rh(CO)2(a) + C3H6(a/g) has been studied on Ni(110), Ni(100) and ZnO(101BAR0) mainly by HREELS and TPRS. On Ni(110), p(2 x 1)-OH(a) was completely diminished by adsorption of Rh(CO)2(pi-C3H5) below 300 K. C3H6 stayed on the surface after this reaction. On Zn(101BAR0) OH(a) was deposited with surface defects indroduced by Ar ion bombardment. The same reaction occurred with OH(a) on ZnO(101BAR0), but not completely on Ni(100) which was covered with oxide layers.
  • A FUKUOKA, T KIMURA, N KOSUGI, H KURODA, Y MINAI, Y SAKAI, T TOMINAGA, M ICHIKAWA
    JOURNAL OF CATALYSIS 126 2 434 - 450 1990年12月 [査読有り][通常論文]
  • M ICHIKAWA, LF RAO, T KIMURA, A FUKUOKA
    JOURNAL OF MOLECULAR CATALYSIS 62 1 15 - 35 1990年09月 [査読有り][通常論文]
  • LF RAO, A FUKUOKA, N KOSUGI, H KURODA, M ICHIKAWA
    JOURNAL OF PHYSICAL CHEMISTRY 94 13 5317 - 5327 1990年06月 [査読有り][通常論文]
  • LF RAO, A FUKUOKA, N KOSUGI, H KURODA, M ICHIKAWA
    JOURNAL OF PHYSICAL CHEMISTRY 94 13 5317 - 5327 1990年06月 [査読有り][通常論文]
  • T FUJIMOTO, A FUKUOKA, M ICHIKAWA
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY 199 149 - COLL 1990年04月 [査読有り][通常論文]
  • FS XIAO, A FUKUOKA, W HENDERSON, DF SHRIVER, M ICHIKAWA
    CATALYSIS LETTERS 6 3-6 361 - 368 1990年 [査読有り][通常論文]
  • T KIMURA, A FUKUOKA, M ICHIKAWA
    CATALYSIS LETTERS 4 4-6 279 - 285 1990年 [査読有り][通常論文]
  • M TANAKA, Y SAKAI, T TOMINAGA, A FUKUOKA, T KIMURA, M ICHIKAWA
    JOURNAL OF RADIOANALYTICAL AND NUCLEAR CHEMISTRY-LETTERS 137 4 287 - 297 1989年11月 [査読有り][通常論文]
  • M ICHIKAWA, PE HOFFMANN, A FUKUOKA
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS 18 1395 - 1396 1989年09月 [査読有り][通常論文]
  • T FUJIMOTO, A FUKUOKA, J NAKAMURA, M ICHIKAWA
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS 13 845 - 848 1989年07月 [査読有り][通常論文]
  • T FUJIMOTO, A FUKUOKA, J NAKAMURA, M ICHIKAWA
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS 13 845 - 848 1989年07月 [査読有り][通常論文]
  • 福岡 淳, 饒 凌芬, 市川 勝
    日本化学会誌 1989 3 561 - 568 日本化学会 1989年03月 [査読有り][通常論文]
  • A FUKUOKA, LF RAO, M ICHIKAWA
    NIPPON KAGAKU KAISHI 3 561 - 568 1989年03月 [査読有り][通常論文]
  • LF RAO, A FUKUOKA, M ICHIKAWA
    ACID-BASE CATALYSIS 341 - 348 1989年 [査読有り][通常論文]
  • Rao L.?F, Guo X.?X, Fukuoka A, Ichikawa W
    Acta Chimica Sinica English Edition 7 5 477 - 479 1989年 [査読有り][通常論文]
  • Atsushi Fukuoka, Takuma Kimura, Ling-Fen Rao, Masaru Ichikawa
    Catalysis Today 6 1-2 55 - 62 1989年 [査読有り][通常論文]
     
    RhFe and PdFe bimetallic catalysts were prepared from carbonyl clusters such as [Fe2Rh4(CO)16]2- and [Fe6Pd6(CO)24]3- grafted on SiO2. They exhibited high activities and selectivities for C1+C2 alcohol formation from CO+H2. The RhFe catalysts also provided high activities for alcohol formation in hydroformylation of ethene and propene. On the H2-reduced catalyst, Mo{combining double acute accent}ssbauer and EXAFS studies suggest that RhFe and PdFe bimetallic sites are dispersed on the SiO2 surface, with direct MFe3+O (M = Pd) bondings. In IR spectrum of chemisorbed CO on the Fe2Rh4/SiO2, a band appeared which is reasonably assigned to μ2:η2CO coordinating to the RhFe3+ site. Promoting effect of Fe is discussed in terms of the two-site activation of CO insertion on bimetallic RhFe3+ and PdFe3+ sites derived from RhFe and PdFe carbonyl clusters. © 1989.
  • T KIMURA, A FUKUOKA, A FUMAGALLI, M ICHIKAWA
    CATALYSIS LETTERS 2 4 227 - 233 1989年 [査読有り][通常論文]
  • M ICHIKAWA, LF RAO, T ITO, A FUKUOKA
    FARADAY DISCUSSIONS 87 321 - 336 1989年 [査読有り][通常論文]
  • M ICHIKAWA, LF RAO, T ITO, A FUKUOKA
    FARADAY DISCUSSIONS 87 321 - 336 1989年 [査読有り][通常論文]
  • Masaru Ichikawa, Pedro E. Hoffmann, Atushi Fukuoka
    Journal of the Chemical Society, Chemical Communications 18 1395 - 1396 1989年 [査読有り][通常論文]
     
    I.r. spectroscopic evidence demonstrates the low frequency band of both C- and O-ended CO which interacts with Rh and a promoter Mn ion on a Rh-Mn/SiO < inf> 2< /inf> catalyst in the chemisorption and exchange of CO using < sup> 13< /sup> CO and C< sup> 18< /sup> O.
  • K MACHIDA, A FUKUOKA, M ICHIKAWA, M ENYO
    NIPPON KAGAKU KAISHI 8 1426 - 1432 1988年08月 [査読有り][通常論文]
  • H MATSUZAKA, A FUKUOKA, Y KOYASU, M UE, M ORISAKU, M HIDAI
    NIPPON KAGAKU KAISHI 1988 5 705 - 713 1988年05月 [査読有り][通常論文]
  • LF RAO, A FUKUOKA, M ICHIKAWA
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS 7 458 - 460 1988年04月 [査読有り][通常論文]
  • LF RAO, A FUKUOKA, M ICHIKAWA
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS 7 458 - 460 1988年04月 [査読有り][通常論文]
  • A FUKUOKA, T KIMURA, M ICHIKAWA
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS 6 428 - 430 1988年03月 [査読有り][通常論文]
  • A FUKUOKA, T KIMURA, M ICHIKAWA
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS 6 428 - 430 1988年03月 [査読有り][通常論文]
  • A FUKUOKA, M ICHIKAWA, JA HRILJAC, DF SHRIVER
    INORGANIC CHEMISTRY 26 22 3643 - 3645 1987年11月 [査読有り][通常論文]
  • A FUKUOKA, M ICHIKAWA, JA HRILJAC, DF SHRIVER
    INORGANIC CHEMISTRY 26 22 3643 - 3645 1987年11月 [査読有り][通常論文]
  • K MACHIDA, A FUKUOKA, M ICHIKAWA, M ENYO
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS 19 1486 - 1487 1987年10月 [査読有り][通常論文]
  • K MACHIDA, A FUKUOKA, M ICHIKAWA, M ENYO
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS 19 1486 - 1487 1987年10月 [査読有り][通常論文]
  • A FUKUOKA, H MATSUZAKA, M HIDAI, M ICHIKAWA
    CHEMISTRY LETTERS 5 941 - 944 1987年 [査読有り][通常論文]
  • M HIDAI, A FUKUOKA, Y KOYASU, Y UCHIDA
    JOURNAL OF MOLECULAR CATALYSIS 35 1 29 - 37 1986年04月 [査読有り][通常論文]
  • 福岡 淳, 市川 勝
    表面科学 7 2 157 - 167 The Surface Science Society of Japan 1986年 
    In homogeneous catalysis, bimetallic cluster compounds, possibly as catalytic active species, are expected to provide a synergistic effect for the catalytic activity because of the multi-centered metal atoms simultaneously involved in the catalytic reactions, e.g. CO+H2 into ethylene glycol or olefin hydroformylation. In some cases, metal clusters are easily decomposed into lower-nuclear subclusters as well as mononuclear species under the prevailing reaction conditions. On the other hand, bimetallic carbonyl clusters are used as a precursor to form a surface supported bimetallic ensembles having a high dispersion and well-defind metal compositions. Comparing with the conventionally prepared alloy catalysts, they exhibit a unique catalytic performance in effectively promoting the catalytic activity and in modifying the selectivity in some typical catalytic reactions such as CO+H2 reaction and olefin hydroformylation. The catalysis by supported bimetallic clusters is discussed in terms of their unique structural properties, morphologies, metal compositions and electronic interaction with metal oxides, carbon and polymers, which are studied by the different physical techniques such as EXAFS, Mössbauer, IR, NMR and XPS.
  • Y KOYASU, A FUKUOKA, Y UCHIDA, M HIDAI
    CHEMISTRY LETTERS 7 1083 - 1086 1985年 [査読有り][通常論文]
  • M HIDAI, A FUKUOKA, Y KOYASU, Y UCHIDA
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS 8 516 - 517 1984年 [査読有り][通常論文]

書籍

  • バイオリファイナリー触媒技術の新展開
    シーエムシー出版 2011年
  • 触媒調製ハンドブック
    エヌ・ティー・エス 2011年
  • 触媒調製ハンドブック
    エヌ・ティー・エス 2011年
  • New Development of Biomass-refinery Catalytic Technology
    CMC Books 2011年
  • Handbook of Catalyst Preparation
    NTS 2011年
  • Handbook of Catalyst Preparation
    NTS 2011年
  • Thermochemical Conversion of Biomass to Liquid Fuels and Chemicals
    RSC Publishing 2010年
  • レアメタル便覧
    丸善 2010年
  • 現代界面コロイド科学の事典
    丸善 2010年
  • Handbook of Rare Metals
    Maruzen 2010年
  • Dictionary of modern interfacial colloid science
    Maruzen 2010年
  • Catalysis of Mesoporous Solid Acids for Environmentally Benign Processes
    American Scientific Publisher 2009年
  • 木質系有機資源の新展開Ⅱ
    シーエムシー出版 2009年
  • New development of plant organic resources
    CMC Publication 2009年
  • 金属成分の担持法
    講談社サイエンティフィク 2008年
  • Metal nanoclusters in catalysis and materials science: the issue of size-control
    Elsevier 2007年
  • 植物由来プラスチックの高機能化とリサイクル技術
    サイエンス&テクノロジー 2007年
  • 環境調和型新材料シリーズ 触媒材料
    日刊工業新聞社 2007年
  • バイオ液体燃料
    エヌ・ティー・エス 2007年
  • Morphology Control of Materials and Nanoparticles. Advanced Materials Processing and Characterization
    Springer-Verlag 2003年
  • Synthesis of Organometallic Compounds -A Practical Guide
    Wiley 1997年

講演・口頭発表等

その他活動・業績

特許

受賞

  • 2022年05月 公益社団法人石油学会 学会賞
     セルロース・キチンの触媒変換による有用化学品合成に関する先導的研究 
    受賞者: 福岡淳
  • 2020年09月 井上春成賞委員会 井上春成賞
     青果物鮮度保持用プラチナ触媒の開発 
    受賞者: 福岡淳;谷口潤
  • 2017年01月 北海道大学 研究総長賞優秀賞
     
    受賞者: 福岡 淳
  • 2015年07月 公益財団法人新化学技術推進協会 第14回グリーン・サスティナブルケミストリー賞文部科学大臣賞
     固体触媒によるセルロース系バイオマス分解の先導的研究 
    受賞者: 福岡淳
  • 2015年03月 北海道大学 研究総長賞優秀賞
     
    受賞者: 福岡 淳
  • 2015年03月 触媒学会 学会賞(学術部門)
     固体触媒によるセルロース分解の研究 
    受賞者: 福岡 淳
  • 2009年11月 台湾国家科学委員会化学研究推動中心レクチャーシップ
  • 1995年05月 山下太郎顕彰育成会 山下太郎学術研究奨励賞
     金属クラスター錯体の触媒作用に関する研究 
    受賞者: 福岡 淳
  • 1994年04月 触媒学会 奨励賞
     異種金属クラスター担持触媒の構造と反応特性に関する研究 
    受賞者: 福岡 淳

共同研究・競争的資金等の研究課題

  • キチンを再生可能炭素・窒素資源として利用するための効率的な触媒反応法の開発
    日本学術振興会:科学研究費助成事業 基盤研究(B)
    研究期間 : 2021年04月 -2024年03月 
    代表者 : 小林 広和, 福岡 淳, 佐川 拓矢
  • 固体触媒による結晶セルロース分解
    日本学術振興会:科学研究費助成事業 基盤研究(B)
    研究期間 : 2021年04月 -2024年03月 
    代表者 : 福岡 淳, 小林 広和, 宋 志毅
  • 炭素系触媒によるリグノセルロース分解
    科学技術振興機構:先端的低炭素化技術開発(ALCA)
    研究期間 : 2013年10月 
    代表者 : 福岡 淳
  • 文部科学省:科学研究費補助金(基盤研究(S))
    研究期間 : 2008年 -2012年 
    代表者 : 福岡 淳, 小林 広和, 原 賢二, 小林 広和
     
    石油資源の減少や二酸化炭素排出による地球温暖化対策のために、再生可能エネルギーであるバイオマスから燃料や化学品を合成が切望されている。本研究では、豊富かつ食料と競合しないバイオマスであるリグノセルロース(セルロース、ヘミセルロース、リグニン)の有効利用方法として、リグノセルロースを分解し化学品を合成するための新たな触媒と反応を開発するとともに、活性点の構造解析と反応機構の解明を行った。
  • 文部科学省:科学研究費補助金(特定領域研究)
    研究期間 : 2006年 -2009年 
    代表者 : 福岡 淳, 原 賢二, 小林 広和
     
    本研究では、ゼオライトやメソポーラスシリカなどのミクロ・メソポーラス物質の規則性ナノ空間内で新規金属ナノクラスターを鋳型合成し、金属クラスターとポーラス物質の協奏機能により新しい分子変換機能を創出することを目的とした。白金ナノ粒子担持触媒を用いた水素中微量一酸化炭素選択酸化(PROX)反応では、細孔径4.0ナノメートルのFSM-22が細孔活性を示すという触媒活性の細孔径依存性についての知見を得た。その他にも、メソポーラスシリカが単なるメソ空間としてではなく、金属種との協奏的な触媒機能を発現する構造体であることを示す結果を得た。また、表面シラノール基を選択的に有機修飾するためにメソポーラスシリカの外表面上のシラノールをシリル化剤で修飾し、詳細な構造解析を行った。さらに、内表面に銅錯体を導入してフェノール誘導体の酸化的重合反応に適用した。
  • 文部科学省:科学研究費補助金(基盤研究(C))
    研究期間 : 2006年 -2007年 
    代表者 : 福岡 淳, 岩佐 信弘
     
    まず初年度に、金属ナノ粒子の鋳型合成と構造同定について検討を行った。メソポーラスシリカ(FSM-16、MCM-41)を担体として、細孔内で白金ナノ粒子を鋳型合成した。電子顕微鏡などの構造解析から、細孔径の大きさに対応したナノ粒子が生成していることを確認した。次に、これらを触媒に用いて燃料電池用水素中の微量CO選択酸化反応(PROX)における活性評価を行った。その結果、FSM-16担持白金ナノ粒子が、先行触媒よりもはるかに優れた活性・選択性・寿命を示すことを見出した。次年度には、PROX反応の機構研究と、オレフィン酸化反応における活性評価を行った。白金ナノ粒子/FSM-16触媒上にCOを吸着させると、気相中にCO_2が少量生成することを赤外分光法で見いだした。ここに重酸素(^<18>O_2)を加えると、CO_2中に^<18>Oは取り込まれずC^<16>O_2が生成した。さらに重水素(D_2)を導入してPROX条件にしても、C^<16>O_2生成が増大し^<18>Oは含まれなかった。以上の結果から、^<16>O源として担体の酸素がCO酸化に使われることが示唆された。従って、担体上の表面OH基が白金上のCOを攻撃して二酸化炭素と水素を生成する機構であると結論した。また、PROX反応触媒中における白金担持量の低減化を試みたところ、空間速度などの反応条件の最適化によって白金量を0.5〜1重量%にしてもCO完全除去が可能であることを見いだした。さらに、メソポーラスシリカ内に白金、パラジウム、銀のナノ粒子をそれぞれ合成し、エチレンの酸化反応を室温から200℃で検討した。酸素の転化率は100%であったが、エチレンは完全酸化によりCO_2となり、エポキシドなどの有機化合物の生成は認められなかった。従って、選択酸化のためには系中で過酸化水素を発生させる助触媒が必要であると推論した。
  • 固体触媒によるバイオマス変換
    科学研究費補助金
    研究期間 : 2007年
  • Biomass conversion by heterogeneous catalysis
    Grant-in-Aid for Scientific Research
    研究期間 : 2007年
  • 文部科学省:科学研究費補助金(基盤研究(C))
    研究期間 : 2001年 -2002年 
    代表者 : 福岡 淳
     
    メソ細孔シリカ内を鋳型として金属ナノ細線の生成機構、大量合成および分離法の確立を目指した。光還元によるナノ細線の生成機構を種々検討した結果、細孔内で金属イオンの移動速度が還元速度よりも大きいときにナノ細線ができるが、逆の場合にはナノ粒子ができることが示唆された。そこで、水素還元中に水蒸気(室温での蒸気圧、約20Torr)を共存させるとイオン移動が促進され、ナノ細線が生成することを見出した。この方法では操作が簡便であるとともに、金属担持量を上げることができる。このように、金属ナノ細線の簡便な大量合成法を開発することに成功した意義は大きい。白金の他に、パラジウム、ロジウム、白金-金のナノ細線を合成した。特に白金-金の場合には、白金-金合金相の他に、白金相、金相の存在が示唆された。HMM-1からフッ酸処理により分離した白金ナノ細線の構造を透過型電子顕微鏡と走査型トンネル顕微鏡で観察した。細線の直径は3mm長さは25μmに達するものもあり、この場合アスペクト比は8300に達した。またSTM観察から、細線の表面に約3mm周期で凹凸があり、ナノネックレス構造をもつことが実証された。一方、純シリカのFSM-16内で調製した白金ナノ細線の表面は平坦であり、HMM-1の細孔に凹凸構造があることが示唆された。さらに、メソ細孔内での金属ナノ粒子合成に超臨界流体を利用した。メソ細孔シリカを担体として、含浸時に超臨界二酸化炭素処理をすることにより、高分散RhおよびRhPtバイメタリック触媒が得られた。RhPt媒では合金ナノ粒子が細孔内に高分散担持されており、ブタン水素化分解反応において高収率でエタンを生成することが分かった。
  • 文部科学省:科学研究費補助金(基盤研究(C))
    研究期間 : 1999年 -2000年 
    代表者 : 福岡 淳
     
    平成12年度は、メソ細孔シリカFSM-16(細孔径2.7nm)と有機-無機ハイブリッドメソ細孔シリカHMM-1(細孔径3.1nm)を鋳型として、遷移金属ナノ細線を合成し、構造解析、物性と触媒作用を検討した。その結果、以下の知見を新たに得た。1.FSM-16にPt塩を含浸させ乾燥を十分に行うこと、及び光還元時に共存させるアルコールを2-プロパノールからメタノールに替えることで、より長いPtナノ細線を細孔内に合成できるようになった。2.HMM-1を担体としてPtおよびRhナノ細線を細孔内に合成することができた。Rhナノ細線としては初めての例である。3.HMM-1細孔内で、Pt-Rh、Pt-Pdナノ細線に合成することに成功し、これらは結晶性の高い合金ナノ細線であることを示した。合金ナノ細線としては初めての例である。また、HMM-1細孔内のナノ細線は特徴的なナノネックレス構造をもつことを明らかにした。4.Ptナノ細線/FSM-16でブタン水素化分解反応を行うと、ナノ粒子よりも36倍高い水素化分解活性(TOF)を示した。ナノ細線という「形」が水素化分解「機能」を著しく向上させるという興味深い結果を得た。一方、Pt-Rhナノ細線/FSM-16ではイソブタンへの異性化活性が出現した。Pt-Pdナノ細線/HMM-1の低温での磁化率は、Ptナノ細線/HMM-1よりも著しく向上した。これは合金かつナノ細線構造という複合効果によるものである。5.ベンゼン/エタノール混合溶媒中で四級アンモニウム塩を共存させてPtナノ細線/FSM-16を処理すると、一部のPtナノ細線を抽出できることが分かった。これまで、鋳型としてのメソ細孔物質をフッ酸で溶解(破壊)してナノ細線を回収することは行われていたが、非破壊的な回収法である化学的抽出法が可能となった。
  • 文部科学省:科学研究費補助金(重点領域研究)
    研究期間 : 1997年 -1997年 
    代表者 : 福岡 淳, 小宮 三四郎, 平野 雅文, 福岡 淳
     
    遷移金属触媒において異種金属がもたらす協同効果は広く知られている。このような協同効果は異種金属界面という特殊な反応場における相乗効果であると考えられているが、これらを分子レベルで解明した例はほとんど知られていない。本研究では白金を含むヘテロバイメタリック錯体において、白金上のエチル基からのβ水素脱離反応および白金上のヒドリドとアルキンの反応において異種金属が白金に与える影響を分子レベルで解明することに成功した。エチル基を有する白金を含むヘテロバイメタリック錯体の合成は1,2-ビス(ジエチルホスフィノ)エタン(以下、dpeと記す)を持つ単核エチル白金錯体Pt(Et)(I)(dpe)とNa[CpMO(CO)_3]、Na[CpW(CO)_3]またはNa[Co(CO)_4]とのメタセシス反応により合成した[(dpe)EtPt-MoCp(CO)_3,(dpe)EtPt-WCp(CO)_3,(dpe)EtPt-Co(CO)_4]。これらの錯体の加熱によりβ水素脱離反応が進行し、エチレンとそれぞれ対応するヒドリド2核錯体を与えた。また、これらの反応はエチル2核錯体に対して1次反応であった。これらの2核錯体のβ水素脱離反応は単核のエチル白金錯体に比ベて速く進行した。ヒドリド白金モリブデン錯体(dpe)HPt-MoCp(C0)_3は、アセチレンジカルボン酸ジメチルやトランなどの2置換アセチレン誘導体と反応し、HMoCp(CO)_3と0価白金錯体Pt(RC≡CR)(dpe)を与えた。これは我々がすでに報告しているヘテロバイメタリック錯体におけるアルキル基の移動と類似した反応性であり、白金の酸化によりアルキルやヒドリドが隣接した金属に容易に移動することを示している。しかし、1置換アセチレン誘導体であるアセチレンモノカルボン酸エステルやフェニルアセチレンを用いると白金上のヒドリドがアルキンにマルコフニコフ付加しモリブデン上のカルボニルの1つが脱離し、1つが架橋配位した(dpe)Pt(m-CR=CH_2)(m-CO)MoCp(CO)が得られた。
  • メソ多孔体の触媒機能
    科学研究費補助金
    研究期間 : 1997年
  • Catalysis of mesoporous materials
    Grant-in-Aid for Scientific Research
    研究期間 : 1997年
  • 文部科学省:科学研究費補助金(重点領域研究)
    研究期間 : 1996年 -1996年 
    代表者 : 福岡 淳, 平野 雅文, 小宮 三四郎
     
    我々は、有機へテロ二核/クラスター錯体上のアルキル基の反応性に対する異種金属の共同効果について研究している。本年度はパラジウムを含む新規二核錯体の合成・同定とCO挿入の反応性について検討した。PdとMo、W,Coの組み合わせをもち、Pd上にメチル基を有する新規二核錯体の合成を行い、構造解析を行った。X線構造解析から、(dpe)MePd-Co(CO)_4(1)のPd周りは平面四配位、Co周りは歪んだ三方両錐型の構造であることがわかった。さらにCo上のCO配位子のうち、ひとつがベントセミブリッジング型であることがわかった。錯体1をCOと反応させるとPd-Me間にCOが挿入したアセチル二核錯体が収率良く得られた。類縁化合物と反応速度の比較を行うと、錯体1はPdMeCl(dpe)や(dpe)MePt-Co(CO)_4よりも高い反応性を示すことがわかった。ここで、Na[Co(CO)_4]添加によっても反応速度の阻害がみられなかったことから、反応中、Pd-Co結合は保持されているものと考えられる。さらに、^<13>COを用いて反応を行ったところ、アセチル炭素の^<12>C/^<13>C比は2.0-2.5となり、^<12>COが多いことがわかった。系中に^<12>COが4等量存在し、^<13>COが27等量存在することを考えると、もし反応中にスクランブリングが起これば^<12>C/^<13>比は0.15になるはずである。従って、上の結果はCo上のCO配位子が優先的にPd-Me間に挿入することを示している。これはPdとCoの共同効果によるものと推定される。今後は触媒反応への展開を行いたい。
  • 文部科学省:科学研究費補助金(重点領域研究)
    研究期間 : 1995年 -1995年 
    代表者 : 福岡 淳, 平野 雅文, 小宮 三四郎
     
    今年度は新規有機ヘテロ2核/クラスター錯体として、エチル基と1,2-ビス(ジフェニルホスフィノ)エタン(以下dpeと略)を配位子をもちPtとMo、W、Mn、Coの組み合わせからなる二核錯体の合成を行った。さらにPd上にメチル基をもち、Mo、W、Coを含む二核錯体を合成・単離することができた。また、ナフサ改質触媒のモデルとなる有機Pt-Re-S錯体の合成を行った。さらに、チオラト基を有するチタノセン錯体とノルボナジエン配位子をもつ有機Pt錯体との反応により、チオラト配位子がPtとTiに架橋した2核錯体の合成・単離に成功した。錯体の同定はIR、NMR、元素分析、化学反応性により行った。ここで、(dpe)MePd-Co(CO)_4、Me_2Pt(μ-SMe)_2TiCp_2および有機Pt-Re-S錯体では良好な単結晶が得られ、X線構造解析により分子構造を決定することができた。メチル基とPdを含む(dpe)MePd-Co(CO)_4では室温、1気圧という条件下でCO挿入反応が進行し対応するアシル2核錯体を収率80%で与えた。また、CO挿入反応はCo(CO)_4部分により促進されることがわかった。さらに、dpeを配位子としてエチル基とPtを含む二核錯体では、熱分解条件下で還元的脱離よりもβ-水素脱離が速やかに進行し、エチレンを生成することを見いだした。特に、Pt-Mo、Pt-W錯体ではエチレンとともに対応するヒドリド二二核錯体が生成し、これを単離・同定した。この反応は二核構造を保持したままβ-水素脱離が進行する例である。動力学的な検討から、このβ-水素脱離反応は会合型機構で進行するものと推測された。
  • 文部科学省:科学研究費補助金(奨励研究(A))
    研究期間 : 1993年 -1994年 
    代表者 : 福岡 淳
     
    本研究では、担持金属触媒のモデルとなる錯体を合成し、触媒反応特性に大きな影響を与える金属-担体相互作用の本質に関する分子レベルでの検討を行うこと、およびその錯体を用いた触媒反応を行うことを目的とした。まず、シリカ担持白金触媒のモデルとして、単核および複核の有機白金シロキソ錯体PtMe(OSiPh_3)(cod)(1)と[((cod)MePtO)SiPh_2]_2O(2)を合成した。新規錯体1,2の構造はIR、NMR、元素分析、化学反応により行った。また、1の分子構造はX線構造解析により決定した。錯体1は室温以下、1気圧の水素雰囲気下で容易に還元され、配位子の水素化物と白金コロイドを与えることを見出した。この白金コロイドを透過型電子顕微鏡で観察すると、その粒子径は5-10nmであることがわかった。この還元反応を利用して、錯体1をアルミナ表面に含浸担持させ、溶液中で水素と反応させることにより、温和な条件下でPt/Al_2O_3(3)が得られた。透過型電子顕微鏡の観察から白金の粒子径は約8nmで、塩化白金酸から通常法で調製したPt/Al_2O_3(4)に比べ、より白金が均一に分散していることが分かった。3による1,5シクロオクタジエンの水素化反応を行うと部分水素化のみ進行し、シクロオクテンが得られた(収率60%、選択率100%)。一方、4を用いた場合には完全水素化が進行してしまい、シクロオクタンが得られた(収率100%)。

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  • 分子化学(物質変換化学)
    開講年度 : 2021年
    課程区分 : 修士課程
    開講学部 : 総合化学院
    キーワード : 触媒,触媒化学,資源有効利用,環境問題,グリーン化学
  • 環境と人間
    開講年度 : 2021年
    課程区分 : 学士課程
    開講学部 : 全学教育
    キーワード : 触媒、化学物質、環境とエネルギー、持続的な社会発展
  • 触媒化学
    開講年度 : 2021年
    課程区分 : 学士課程
    開講学部 : 理学部
    キーワード : 触媒,触媒化学,表面科学,高分子化学,理論化学
  • 環境と人間
    開講年度 : 2021年
    課程区分 : 学士課程
    開講学部 : 全学教育
    キーワード : バイオマス、農耕地、食料、エネルギー、有用物質、触媒、バイオエコノミー

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学内役職歴

  • 2014年4月1日 - 2015年3月31日 企画・経営室室員
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委員歴

  • 2021年03月 - 現在   公益社団法人日本化学会   理事
  • 2016年07月 - 現在   国際触媒学会(IACS)   Officer
  • 2018年05月 - 2019年05月   一般社団法人触媒学会   会長
  • 2012年07月 - 2016年07月   国際触媒学会   評議員
  • 2012年03月 - 2013年07月   第16回均一系不均一系触媒国際会議   組織委員長
  • 2008年03月 - 2012年02月   触媒学会   バイオマス変換研究会世話人代表   触媒学会
  • 2004年 - 2005年   ゼオライト学会   理事

社会貢献活動

  • さきがけ領域アドバイザー
    期間 : 2015年04月04日
    役割 : 助言・指導
    主催者・発行元 : 科学技術振興機構
  • JST-ALCA秋鹿分科会及びSIPエネルギーキャリア運営・評価委員会委員
    期間 : 2013年05月01日 - 2015年03月31日
    役割 : 助言・指導
    主催者・発行元 : 科学技術振興機構

学術貢献活動

  • NEDO技術委員
    期間 : 2014年08月01日
    種別 : 学術調査
    主催者・責任者 : NEDO


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