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Development of environmentally benign solid catalysis based on surface dynamic organometallic chemistry

Research Project

Project/Area Number 17H03458
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Catalyst/Resource chemical process
Research InstitutionKagawa University

Principal Investigator

Wada Kenji  香川大学, 医学部, 教授 (10243049)

Co-Investigator(Kenkyū-buntansha) 馮 旗  香川大学, 創造工学部, 教授 (80274356)
吉田 朋子  大阪市立大学, 複合先端研究機構, 教授 (90283415)
Project Period (FY) 2017-04-01 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥17,550,000 (Direct Cost: ¥13,500,000、Indirect Cost: ¥4,050,000)
Fiscal Year 2019: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
Fiscal Year 2018: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Fiscal Year 2017: ¥10,010,000 (Direct Cost: ¥7,700,000、Indirect Cost: ¥2,310,000)
Keywordsグリーンケミストリー / 固体触媒 / 有機金属触媒 / イリジウム / 酸化チタン / 酸化セリウム / 脱水素反応 / C-H結合活性化 / イリジウム錯体 / 脱水素
Outline of Final Research Achievements

In the present study, highly-active environmentally-benign solid catalysts were developed by controlling the dynamic behaviour of organometallic species on the surface of solid crystals.
Rutile-supported Ir catalysts that were effective for the synthesis of benzimidazoles via the dehydrogenative pathway were developed. For the synthesis of benzimidazoles via hydrogen transfer, the Ir catalysts supported on {010}/{101}-faceted anatase showed the excellent activity. Also, the P-modification of titania supports greatly enhanced the activity. The composite catalysts of Ir complexes and ceria that were active and selective for the dehydrogenative silylation of styrenes were developed. The treatment of Ru/CeO2 catalysts with PPh3 and HCHO was an efficient way to generate the active species for hydroarylation of C-C multiple bonds. A novel Fourier-transformed near-infrared imaging spectroscopic system that realized the rapid and direct analysis of organic products was developed.

Academic Significance and Societal Importance of the Research Achievements

従来と比較して飛躍的に貴金属種当たりの活性が高い触媒開発、および温和な条件下での反応を可能にし、かつ回収・再利用が容易な触媒開発に至った。これら開発触媒はいずれも調製が容易で反応後の生成物分離も効率よく行える。さらに希少な貴金属元素の高効率利用を達成しており、有機合成プロセスの簡略化とコスト低減につながることから、産業および元素戦略の双方の観点から波及効果が期待できる。固体表面での有機金属錯体の動的挙動に完全な解明には至っていないが、高活性を引き出すための幾つかの必要要件を明らかにしており、学術的に意義深い。

Report

(4 results)
  • 2019 Annual Research Report   Final Research Report ( PDF )
  • 2018 Annual Research Report
  • 2017 Annual Research Report
  • Research Products

    (27 results)

All 2020 2019 2018 2017

All Journal Article (6 results) (of which Peer Reviewed: 6 results) Presentation (21 results) (of which Int'l Joint Research: 13 results,  Invited: 4 results)

  • [Journal Article] Effect of phosphorus-modification of titania supports on the iridium-catalyzed synthesis of benzimidazoles2020

    • Author(s)
      Yu Han、Wada Kenji、Fukutake Tatsuhiro、Feng Qi、Uemura Shinobu、Isoda Kyosuke、Hirai Tomomi、Iwamoto Shinji
    • Journal Title

      Catalysis Today

      Volume: - Pages: 410-417

    • DOI

      10.1016/j.cattod.2020.02.014

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Titania-supported iridium catalysts for dehydrogenative synthesis of benzimidazoles2020

    • Author(s)
      Wada Kenji、Yu Han、Feng Qi
    • Journal Title

      Chinese Chemical Letters

      Volume: 31 Issue: 3 Pages: 605-608

    • DOI

      10.1016/j.cclet.2019.05.054

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Visualization of Chemical Composition and Chloride Ion Distribution by Novel NIR Imaging Spectroscopic System2019

    • Author(s)
      Wada Kenji、Okazaki Shinichiro、Ishimaru Ichiro
    • Journal Title

      NIHON GAZO GAKKAISHI (Journal of the Imaging Society of Japan)

      Volume: 58 Issue: 6 Pages: 644-650

    • DOI

      10.11370/isj.58.644

    • NAID

      130007760271

    • ISSN
      1344-4425, 1880-4675
    • Year and Date
      2019-12-10
    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Development of titania-supported iridium catalysts with excellent low-temperature activities for the synthesis of benzimidazoles via hydrogen transfer2019

    • Author(s)
      Fukutake Tatsuhiro、Wada Kenji、Yu Han、Hosokawa Saburo、Feng Qi
    • Journal Title

      Molecular Catalysis

      Volume: 477 Pages: 110550-110550

    • DOI

      10.1016/j.mcat.2019.110550

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Generation of Active Ruthenium Catalysts for Hydroarylation of C-C Multiple Bonds from Isolated Ru(IV)=O Species Supported on CeO22018

    • Author(s)
      Miura Hiroki、Nagao Masahiro、Hosokawa Saburo、Shishido Tetsuya、Inoue Masashi、Wada Kenji
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 91 Issue: 9 Pages: 1397-1401

    • DOI

      10.1246/bcsj.20180144

    • NAID

      130007484160

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Striking effects of a titania support on the low-temperature activities of Ir catalysts for the dehydrogenative synthesis of benzimidazole and indole2018

    • Author(s)
      Fukutake Tatsuhiro、Wada Kenji、Liu Gang Chuan、Hosokawa Saburo、Feng Qi
    • Journal Title

      Catalysis Today

      Volume: 303 Pages: 235-240

    • DOI

      10.1016/j.cattod.2017.08.014

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Presentation] Development of reusable composite catalysts for dehydrogenative reactions from Ir complexes and solid metal oxides2019

    • Author(s)
      Daijiro Sorada, Kenji Wada, Qi Feng, Masaaki Nishioka, Ken-ichi Fujita
    • Organizer
      The 17th Korea Japan Symposium on Catalysis
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Effect of phosphorus-modified titania supports on the iridium-catalyzed synthesis of benzimidazoles2019

    • Author(s)
      Han Yu, Kenji Wada, Tatsuhiro Fukutake, Qi Feng, Tomomi Hirai, Shinji Iwamoto
    • Organizer
      The 17th Korea Japan Symposium on Catalysis
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] イリジウム錯体と金属酸化物の複合による再利用可能な脱水素化用触媒の開発2019

    • Author(s)
      空田大地郎・和田健司・馮旗・西岡正明・藤田健一
    • Organizer
      第24回JPIJSポスターセッション
    • Related Report
      2019 Annual Research Report
  • [Presentation] Effect of titania supports on the iridium-catalyzed synthesis of benzimidazoles2019

    • Author(s)
      Han Yu, Kenji Wada, Tatsuhiro Fukutake, Qi Feng, Tomomi Hirai, Shinji Iwamoto
    • Organizer
      The 8th Asia-Pacific Congress on Catalysis
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Rapid and direct visualization of organic compounds/reactions by near infrared imaging spectroscopy2019

    • Author(s)
      Kenji Wada, Tsubasa Saito, Hideya Taniguchi, Ichiro Ishimar
    • Organizer
      14th European Congress on Catalysis
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] イリジウム錯体と金属酸化物の複合による再利用可能な脱水素化用触媒の開発2019

    • Author(s)
      空田大地郎・和田健司・馮旗・西岡正明・藤田健一
    • Organizer
      第13回触媒道場
    • Related Report
      2019 Annual Research Report
  • [Presentation] Rapid and direct visualization of organic compounds/reactions by near infrared imaging spectroscopy2019

    • Author(s)
      Kenji Wada, Tsubasa Saito, Hideya Taniguchi, Ichiro Ishimaru
    • Organizer
      19th International Council for NIR Spectroscopy
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] イリジウム錯体とゼオライトの複合による再利用可能な脱水素反応用触媒の開発2019

    • Author(s)
      空田大地郎・和田健司:馮旗・西岡正明・藤田健一
    • Organizer
      第49回石油・石油化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] イリジウム錯体と金属酸化物の複合による再利用可能な脱水素化用触媒の開発2019

    • Author(s)
      空田大地郎・和田健司:馮旗・西岡正明・藤田健一
    • Organizer
      2019年日本化学会中国四国支部大会 徳島大会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Striking effect of supports on Ir-catalyzed selective organic transformations2019

    • Author(s)
      Kenji Wada
    • Organizer
      The 2nd BK 21+ International Symposium on Photo-Bio-Chemistry
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Low-Temperature Activities of Titania-supported Iridium Catalysts for the Synthesis of Benzimidazoles via Hydrogen Transfer2018

    • Author(s)
      Kenji Wada
    • Organizer
      2018 International Symposium on Advancement and Prospect of Catalysis Science & Technology
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 固体表面・金属種間の相互作用を活かした有機合成用固体触媒の開発2018

    • Author(s)
      和田健司
    • Organizer
      第1回 物質エネルギー化学懇談会
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] Striking effects of ceria on iridium catalysts for the dehydrogenative silylation of styrenes: Facile in situ preparation of solid catalysts2018

    • Author(s)
      Kenji Wada, Daijiro Sorada, Qi Feng, Saburo Hosokawa
    • Organizer
      3rd Fundamentals and Applications of Cerium Oxide in Catalysis
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Active, Selective, and Recyclable Iridium Catalysts for Dehydrogenative Silylation of Styrenes Prepared in situ from Ir Complexes and Metal Oxides2018

    • Author(s)
      Kenji Wada, Daijiro Sorada, Qi Feng
    • Organizer
      18th International Symposium on Relations between Homogeneous and Heterogeneous Catalysis
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Striking Effect of Titania Supports on Ir-Catalyzed Synthesis of Benzimidazoles via Dehydrogenation or Hydrogen Transfer2018

    • Author(s)
      Kenji Wada, Tatsuhiro Fukutake, Qi Feng
    • Organizer
      The 8th Tokyo Conference on Advanced Catalytic Science and Technology
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Rapid and direct visualization of organic compounds/reactions by near infrared imaging spectroscopy2018

    • Author(s)
      Kenji Wada, Hideya Taniguchi, Ichiro Ishimaru
    • Organizer
      The International Symposium on Catalysis and Fine Chemicals 2018
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] イリジウム錯体・セリア複合触媒によるスチレン類の脱水素シリル化反応2018

    • Author(s)
      空田大地郎、和田健司、馮 旗
    • Organizer
      第121回触媒討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Effect of Titania Supports on Ir-Catalyzed Synthesis of Benzimidazoles via Dehydrogenation or Hydrogen Transfer2017

    • Author(s)
      Kenji Wada, Tatsuhiro Fukutake, Qi Feng
    • Organizer
      16th Korea-Japan Symposium on Catalysis & 3rd International Symposium of Institute for Catalysis
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Effect of Crystalline Structure of Titania Support on Ir-Catalyzed Synthesis of Nitrogen-containing Chemicals2017

    • Author(s)
      Kenji Wada, Tatsuhiro Fukutake, Qi Feng
    • Organizer
      13th European Congress on Catalysis (EUROPACAT2017)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 固体表面・金属種間の相互作用を活かした有機合成用触媒の開発2017

    • Author(s)
      和田健司
    • Organizer
      日本化学会中国四国支部 徳島地区化学講演会「四国からの触媒科学の新展開」
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] 水素移動型含窒素有機化合物合成反応に有効な担持イリジウム触媒の開発2017

    • Author(s)
      福武龍宙、和田健司、馮旗
    • Organizer
      石油学会第66回研究発表会
    • Related Report
      2017 Annual Research Report

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Published: 2017-04-28   Modified: 2021-02-19  

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