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2013 Fiscal Year Annual Research Report

ナノリアクター触媒の開発と反応集積化への展開

Publicly Offered Research

Project AreaOrganic Synthesis based on Integration of Chemical Reactions. New Methodologies and New Materials
Project/Area Number 24106702
Research InstitutionTohoku University

Principal Investigator

浅尾 直樹  東北大学, 原子分子材料科学高等研究機構, 教授 (60241519)

Project Period (FY) 2012-04-01 – 2014-03-31
Keywords多孔質 / 金触媒 / 反応集積化
Research Abstract

ナノサイズの細孔を有する多孔質金属材料は、広い表面積と特異な物性を示すことから、様々な分野で注目されている。申請者は24年度の研究から、ナノ多孔質金材料がメタノールを用いたアミンの直接ホルミル化反応において、優れた触媒として機能することを見出した。これは、気相、液相、固相が関与した三相同一時空間反応集積化の例として注目される。そこで25年度は、本材料を用いた末端アルキンへのヒドロシリル化反応に注目し、本材料のナノスケールの細孔という特殊な空間が、反応に及ぼす影響について検討を行った。本反応は、α体、β-(E)体、β-(Z)体という3つの異性体の生成が可能であり、その制御が問題となる。そこで金‐アルミニウムから作成したナノ多孔質金材料を触媒として用いたところ、β-(E)体が高選択的に得られ、他の異性体はほとんど生成しなかった。本触媒はナノ構造を有しているにもかかわらず耐久性に優れ、繰り返し反応を行っても触媒活性や構造に変化は見られなかった。興味深いことに、本反応は金銀合金リボンから作成した多孔質金では触媒活性が大きく低下することが分かった。この両者の活性の違いは、残存するAlまたはAgの影響によると考えられる。そこで次に、三元系合金であるAu-Ag-Al合金リボンを作成し、詳細な検討を行ったところ、微量に存在する銀が反応を阻害していることを明らかにした。これは、昨年度のアミンの直接ホルミル化反応で得られた結果とは異なるものであり、これら金属間のシナジー効果は反応ごとに与える影響が大きく異なることを明らかにした。

Current Status of Research Progress
Reason

25年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

25年度が最終年度であるため、記入しない。

  • Research Products

    (44 results)

All 2014 2013

All Journal Article (14 results) (of which Peer Reviewed: 12 results) Presentation (28 results) (of which Invited: 1 results) Book (2 results)

  • [Journal Article] Fabrication of Pd-Ni-P Metallic Glass Nanoparticles and Their Application as Highly Durable Catalysts in Methanol Electro-oxidation2014

    • Author(s)
      Zhao, M.; Abe, K.; Yamaura, S.; Yamamoto, Y.; Asao, N.
    • Journal Title

      Chem. Mater.

      Volume: 26 Pages: 1056 - 1061

    • DOI

      10.1021/cm403185h

    • Peer Reviewed
  • [Journal Article] The synergistic effect of nanoporous AuPd alloy catalysts on highly chemoselective 1,4-hydrosilylation of conjugated cyclic enones2014

    • Author(s)
      Chen, Q.; Tanaka, S.; Fujita, T.; Chen, L.; Minato, T.; Ishikawa, Y.; Chen, M.; Asao, N.; Yamamoto, Y.; Jin, T.
    • Journal Title

      Chem. Commun.

      Volume: 50 Pages: 3344 - 3346

    • DOI

      10.1039/c3cc49524h

    • Peer Reviewed
  • [Journal Article] Metal-Catalyzed Annulation Reactions for p-Conjugated Polycycles2014

    • Author(s)
      Jin, T.; Zhao, J.; Asao, N.; Yamamoto, Y.
    • Journal Title

      Chem. Eur. J.

      Volume: 20 Pages: 3554 - 3576

    • DOI

      10.1002/chem.201304640

    • Peer Reviewed
  • [Journal Article] Thieno[2,3-a]carbazole-based donorepeacceptor organic dyes for efficient dyesensitized solar cells2014

    • Author(s)
      Zhao, J.; Jin, T.; Islam, A.; Kwon, E.; Akhtaruzzaman, Md.; Asao, N.; Han, L.; Alamry, K. A.; Kosa, S. A.; Asiri, A. M.; Yamamoto, Y.
    • Journal Title

      Tetrahedron

      Volume: 印刷中 Pages: 印刷中

    • DOI

      10.1016/j.tet.2014.01.001

    • Peer Reviewed
  • [Journal Article] Cu-Catalyzed C-H Amination of Hydrofullerenes Leading to 1,4-Difunctionalized Fullerenes2014

    • Author(s)
      Si, W.; Lu, S.; Bao, M.; Asao, N.; Yamamoto, Y.; Jin, T.
    • Journal Title

      Org. Lett.

      Volume: 16 Pages: 620 - 623

    • DOI

      10.1021/ol403573r

    • Peer Reviewed
  • [Journal Article] Nanoporous gold as an effective catalyst for molecular transformations2013

    • Author(s)
      Asao, N.; Jin, T.
    • Journal Title

      Shokubai

      Volume: 55 Pages: 209 - 213

  • [Journal Article] Remarkable Catalytic Property of Nanoporous Gold on Activation of Diborons for Direct Diboration of Alkynes2013

    • Author(s)
      Chen, Q.; Zhao, J.; Ishikawa, Y.; Asao, N.; Yamamoto, Y.; Jin, T.
    • Journal Title

      Org. Lett.

      Volume: 15 Pages: 5766 - 5769

    • DOI

      10.1021/ol4028013

    • Peer Reviewed
  • [Journal Article] Pd-Catalyzed Cascade Crossover Annulation of o-Alkynylarylhalides and Diarylacetylenes Leading to Dibenzo[a,e]pentalenes2013

    • Author(s)
      Zhao, J.; Oniwa, K.; Asao, N.; Yamamoto, Y.; Jin, T.
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 135 Pages: 10222 - 10225

    • DOI

      10.1021/ja403382d

    • Peer Reviewed
  • [Journal Article] Selective Aerobic Oxidation of Methanol in the Coexistence of Amines by Nanoporous Gold Catalyst: Highly Efficient Synthesis of Formamides2013

    • Author(s)
      Tanaka, S.; Minato, T.; Ito, E.; Hara, M.; Kim, Y.; Yamamoto, Y.; Asao, N.
    • Journal Title

      Chem. Eur. J.

      Volume: 19 Pages: 11832 - 11836

    • DOI

      10.1002/chem.201302396

    • Peer Reviewed
  • [Journal Article] Photo-response on the desorption of an atomic hydrogen on titanium dioxide surface induced by a tip of scanning tunneling microscope2013

    • Author(s)
      Minato, T.; Asao, N.; Yamamoto, Y.; Kawai, M.; Kim, Y.
    • Journal Title

      Chem. Lett.

      Volume: 42 Pages: 942 - 943

    • DOI

      10.1246/cl.130462

    • Peer Reviewed
  • [Journal Article] Selective hydrosilylation of alkynes with nanoporous gold catalyst, Atomic origin of the high catalytic activity of nanoporous gold2013

    • Author(s)
      Ishikawa, Y.; Yamamoto, Y.; Asao, N.
    • Journal Title

      Catal. Sci. Tech.

      Volume: 3 Pages: 2902 - 2905

    • DOI

      10.1039/c3cy00242j

    • Peer Reviewed
  • [Journal Article] Single crystal biphenyl end-capped furan-incorporated oligomers: influence of unusual packing structure on carrier mobility and luminescence2013

    • Author(s)
      Oniwa, K.; Kanagasekaran, T.; Jin, T.; Akhtaruzzaman, M.; Yamamoto, Y.; Tamura, H.; Hamada, I.; Shimotani, H.; Asao, N.; Ikeda, S.; Tanigaki, K.
    • Journal Title

      J. Mater. Chem. C

      Volume: 1 Pages: 4163 - 4170

    • DOI

      10.1039/c3tc30220b

  • [Journal Article] Theoretical Analysis on the Optoelectronic Properties of Single Crystals of Thiophene-furan-phenylene Co-Oligomers: Efficient Photoluminescence due to Molecular Bending2013

    • Author(s)
      Tamura, H.; Hamada, I.; Shang, H.; Oniwa, K.; Akhtaruzzaman, M.; Jin, T.; Asao, N.; Yamamoto, Y.; Kanagasekaran, T.; Shimotani, H.; Ikeda, S.; Tanigaki, K.
    • Journal Title

      J. Phys. Chem. C

      Volume: 117 Pages: 8072 - 8078

    • DOI

      10.1021/jp400646n

    • Peer Reviewed
  • [Journal Article] Alkaline peroxide treatment induces acquired unruly hair by apparently affecting distinct macrofibrils2013

    • Author(s)
      Nawa, T.; Kawaguchi, A.; Kitano, H.; Yamamoto, T.; Fujinami, S.; Asao, N.; Nakajima, K.
    • Journal Title

      J. Cosmet. Sci.

      Volume: 64 Pages: 261 - 271

    • Peer Reviewed
  • [Presentation] Fabrication of Pd-Ni-P Metallic Glass Nanoparticles and Their Application to Methanol Electro-oxidation as Highly Durable Catalysts2014

    • Author(s)
      Zhao, M.; Abe, K.; Yamaura, S.; Yamamoto, Y.; Asao, N.
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋
    • Year and Date
      20140327-20140330
  • [Presentation] パラジウム触媒を用いたオルトアルキニルアリールハライドとジアリールアセチレンの連続的環化反応によるジベンゾペンタレンの構築2014

    • Author(s)
      趙 健・男庭 一輝・浅尾 直樹・山本 嘉則・金 鉄男
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋
    • Year and Date
      20140327-20140330
  • [Presentation] ビチアゾール骨格を有する新規オリゴマー有機半導体の開発2014

    • Author(s)
      菊池洋匡・男庭一輝・金鉄男・下谷秀和・谷垣勝己・山本嘉則・浅尾直樹
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋
    • Year and Date
      20140327-20140330
  • [Presentation] n-型特性の向上を目指した新規ルブレン誘導体の合成と評価2014

    • Author(s)
      武藤裕孝・高野与一・男庭一輝・金鉄男・下谷秀和・谷垣勝巳・山本嘉則・浅尾直樹
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋
    • Year and Date
      20140327-20140330
  • [Presentation] 末端にビフェニ基を有するオリゴセレノフェンの合成と電界効果トランジスタへの応用2014

    • Author(s)
      男庭 一輝・金 鉄男・下谷 秀和・谷垣 勝己・浅尾 直樹・山本 嘉則
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋
    • Year and Date
      20140327-20140330
  • [Presentation] Selective Hydrogenation of Nitroarenes Catalyzed by Pd-based Alloy Nanoparticles2014

    • Author(s)
      Yang, L.; Zhao, M.; Asao, N.
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋
    • Year and Date
      20140327-20140330
  • [Presentation] ナノ多孔質金触媒を用いたアルキンの選択的水素移動部分還元反応2014

    • Author(s)
      Wagh, Y. S.・浅尾 直樹
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋
    • Year and Date
      20140327-20140330
  • [Presentation] Pd 系アモルファス合金ナノワイヤー触媒を用いた鈴木カップリング反応2014

    • Author(s)
      江村 奈津子・柳沼 晋・中山 幸仁・浅尾 直樹
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋
    • Year and Date
      20140327-20140330
  • [Presentation] Nanoporous Gold as a Highly Active Catalyst for Aerobic Oxidation of Hydroxylamines into Nitrones2014

    • Author(s)
      Kusuma, I.; Yudha, S.; Asao, N.
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋
    • Year and Date
      20140327-20140330
  • [Presentation] ブレンステッド酸触媒を用いたアルキニルボロナートの選択的ヒドロホウ素化反応2014

    • Author(s)
      何 漢雍・浅尾 直樹・山本 嘉則・金 鉄男
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋
    • Year and Date
      20140327-20140330
  • [Presentation] NBS を用いたフラーレンモノラジカルの酸化反応による1,4―二置換フラーレン誘導体の選択的合成2014

    • Author(s)
      司 偉麗・浅尾 直樹・山本 嘉則・金 鉄男
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋
    • Year and Date
      20140327-20140330
  • [Presentation] Remarkable deuterium isotope effect of deuterofullerene acceptors on organic photovoltaic performances2014

    • Author(s)
      Jin, T.; Lu, S.; Yasuda, T.; Si, W.; Oniwa, K.; Han, L.; Asao, N.; Yamamoto, Y.
    • Organizer
      The AIMR International Symposium 2014
    • Place of Presentation
      Sendai
    • Year and Date
      20140217-20140219
  • [Presentation] Nanoporous Gold as an Effective Catalyst for Selective Molecular Transformations2013

    • Author(s)
      Asao, N.
    • Organizer
      Sixth Joint Workshop on Frontier Materials
    • Place of Presentation
      Sendai
    • Year and Date
      20131201-20131205
    • Invited
  • [Presentation] Cu-catalyzed C-H amination of hydrofullerenes leading to 1,4-difunctionalized fullerenes2013

    • Author(s)
      Jin, T.; Si, W.; Lu, S.; Asao, N.; Yamamoto, Y.
    • Organizer
      The Eighth International Symposium on Integrated Synthesis (ISIS-8)
    • Place of Presentation
      Nara
    • Year and Date
      20131129-20131201
  • [Presentation] Direct N-Formylation of Amines with Methanol by Nanoporous Gold Catalyst2013

    • Author(s)
      Asao, N.; Tanaka, S.; Yamamoto, Y.
    • Organizer
      The Eighth International Symposium on Integrated Synthesis (ISIS-8)
    • Place of Presentation
      Nara
    • Year and Date
      20131129-20131201
  • [Presentation] Metallic glass nanoparticles as effective catalysts for selective molecular transformations2013

    • Author(s)
      Asao, N.
    • Organizer
      AIMR-UCL Workshop
    • Place of Presentation
      London, UK
    • Year and Date
      20131121-20131122
  • [Presentation] Nanoporous metal-catalyzed Hydrosilylation of alkyne2013

    • Author(s)
      Ishikawa, Y.; Yamamoto, Y.; Asao, N.
    • Organizer
      International Symposium for the 70th Anniversary of the Tohoku Branch Chemical Society of Japan
    • Place of Presentation
      Sendai
    • Year and Date
      20130928-20130930
  • [Presentation] Nanoporous gold catalyst for highly efficient diborylation of alkyne2013

    • Author(s)
      Chen, Q.; Asao N.; Yamamoto, Y.; Jin, T.
    • Organizer
      International Symposium for the 70th Anniversary of the Tohoku Branch Chemical Society of Japan
    • Place of Presentation
      Sendai
    • Year and Date
      20130928-20130930
  • [Presentation] Fabrication of Metallic Glass Nanoparticles and Their Application to Methanol Electro-oxidation as Highly Durable Catalysts2013

    • Author(s)
      Zhao, M.; Abe, K.; Yamaura, S.; Asao, N.
    • Organizer
      International Symposium for the 70th Anniversary of the Tohoku Branch Chemical Society of Japan
    • Place of Presentation
      Sendai
    • Year and Date
      20130928-20130930
  • [Presentation] Nanoporous GoldCatalyst for Cross-Dehydrogenative Coupling Reaction viaC-H bond Activation2013

    • Author(s)
      Ho, H. E.; Jin, T.; Asao, N.; Yamamoto, Y.
    • Organizer
      International Symposium for the 70th Anniversary of the Tohoku Branch Chemical Society of Japan
    • Place of Presentation
      Sendai
    • Year and Date
      20130928-20130930
  • [Presentation] Copper-Catalyzed Amination of Hydrofullerenes via C-H Functionalization2013

    • Author(s)
      Si, W.; Lu, S.; Asao, N.; Yamamoto, Y.; Jin, T.
    • Organizer
      International Symposium for the 70th Anniversary of the Tohoku Branch Chemical Society of Japan
    • Place of Presentation
      Sendai
    • Year and Date
      20130928-20130930
  • [Presentation] Cu-catalyzed C-H amination of hydrofullerenes leading to 1,4-difunctionalized fullerenes2013

    • Author(s)
      Si, W.; Lu, S.; Asao, N.; Yamamoto, Y.; Jin, T.
    • Organizer
      10th International Symposium on Carbanion Chemistry (ISCC-10)
    • Place of Presentation
      Kyoto
    • Year and Date
      20130923-20130926
  • [Presentation] Pd-catalyzed cascade crossover-annulation of o-alkynylarylhalides and diarylacetylenes leading to dibenzo[a,e]pentalenes2013

    • Author(s)
      Jin, T.; Zhao, J.; Asao, N.; Yamamoto, Y.
    • Organizer
      第60回有機金属化学討論会
    • Place of Presentation
      東京
    • Year and Date
      20130912-20130914
  • [Presentation] New Organic Functional Materials for Solar Cells2013

    • Author(s)
      Yamamoto, Y.; Jin, T.; Asao, N.
    • Organizer
      246th American Chemical Society National Meeting & Exposition
    • Place of Presentation
      Indianapolis, USA
    • Year and Date
      20130908-20130912
  • [Presentation] Nanoporous gold catalyst for cross-dehydrogenative coupling via C-H bond activation2013

    • Author(s)
      Ho, H. E.; Jin, T.; Asao, N.; Yamamoto, Y.
    • Organizer
      246th American Chemical Society National Meeting & Exposition
    • Place of Presentation
      Indianapolis, USA
    • Year and Date
      20130908-20130912
  • [Presentation] Pd-catalyzed cascade crossover-annulation of o-alkynylarylhalides and diarylacetylenes leading to dibenzo[a,e]pentalenes2013

    • Author(s)
      Jin, T.; Zhao, J.; Oniwa, K.; Asao, N.; Yamamoto, Y.
    • Organizer
      The Sixteenth International Symposium on Relations between Homogeneous and Heterogeneous Catalysis (ISHHC-16)
    • Place of Presentation
      Sapporo
    • Year and Date
      20130804-20130809
  • [Presentation] Nanoporous gold catalyst for selective transformation of alkynes2013

    • Author(s)
      Ishikawa, Y.; Yan, M.; Jin, T.; Yamamoto, Y.; Asao, N.
    • Organizer
      The Sixteenth International Symposium on Relations between Homogeneous and Heterogeneous Catalysis (ISHHC-16)
    • Place of Presentation
      Sapporo
    • Year and Date
      20130804-20130809
  • [Presentation] ナノポーラス金触媒を用いたC-H結合活性化による脱水素化クロスカップリング2013

    • Author(s)
      何 漢雍、金 鉄男、浅尾 直樹、山本 嘉則
    • Organizer
      第24回 万有仙台シンポジウム
    • Place of Presentation
      仙台
    • Year and Date
      20130629-20130629
  • [Book] Gold Catalysis: An Homogeneous Approach2014

    • Author(s)
      Asao, N.; Hatakeyama, N.; Yamamoto, Y.
    • Total Pages
      印刷中
    • Publisher
      Imperial College Press
  • [Book] Transition-Metal-Mediated Aromatic Ring Construction2013

    • Author(s)
      Asao, N.; Ishikawa, Y.
    • Total Pages
      830 (379 - 398)
    • Publisher
      John Wiley & Sons, Inc.

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Published: 2015-05-28  

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