Development of High Performance Polyoxometalate-Based Catalysts‒From Molecular Catalysts to Nano-Structured Catalysts ‒

• Project/Area Number: 24350026
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: The University of Tokyo
• Principal Investigator: MIZUNO Noritaka 東京大学, 工学(系)研究科(研究院), 教授 (50181904)
• Project Period (FY): 2012-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥17,810,000 (Direct Cost: ¥13,700,000、Indirect Cost: ¥4,110,000); Fiscal Year 2014: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000); Fiscal Year 2013: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000); Fiscal Year 2012: ¥11,700,000 (Direct Cost: ¥9,000,000、Indirect Cost: ¥2,700,000)
• Keywords: ポリオキソメタレート / 分子触媒 / ナノ構造体 / 酸化反応 / 新反応開発

Outline of Final Research Achievements

In this study, we have designed an organic solvent-soluble tungstate monomer. The tungstate monomer could act as an efficient catalyst for N-silylation of indoles. By using the tungstate monomer as the precursor, we have successfully synthesized various kinds of lacunary polyoxometalate-based molecular catalysts. They exhibited the high catalytic performance for acylation of alcohols and dehydration of primary amides to nitriles. Furthermore, several high performance solid catalysts could be developed through immobilization or heterogenization of the molecular catalysts.

Research Products

• [Journal Article] Composites of [γ-H2PV2W10O40]3- and [α-SiW12O40]4- supported on Fe2O3 as heterogeneous catalysts for selective oxidation with aqueous hydrogen peroxide (2015)
  • Author(s): Y. Wang, K. Kamata, R. Ishimoto, Y. Ogasawara, K. Suzuki, K. Yamaguchi, N. Mizuno
  • Journal Title: Catal. Sci. Technol. Volume: in press Issue: 5 Pages: 2602-2611
  • DOI: 10.1039/c4cy01693a
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Selective Oxidation with Aqueous Hydrogen Peroxide by [PO4{WO(O2)2}4]3- Supported on Zinc-Modified Tin Dioxide (2015)
  • Author(s): S. Nojima, K. Kamata, K. Suzuki, K. Yamaguchi, N. Mizuno
  • Journal Title: ChemCatChem Volume: 7 Issue: 7 Pages: 1097-1104
  • DOI: 10.1002/cctc.201402975
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] A Basic －7-Charged Germanodecatungstate Efficient for Chemoselective Acylation of Primary Alcohols (2014)
  • Author(s): K. Sugahara, N. Satake, K. Kamata, T. Nakajima, N. Mizuno
  • Journal Title: Angew. Chem. Int. Ed. Volume: 53 Issue: 48 Pages: 13248-13252
  • DOI: 10.1002/anie.201405212
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Highly Selective Epoxidation of Cycloaliphatic Alkenes with Aqueous Hydrogen Peroxide Catalyzed by [PO4{WO(O2)2}4]3-/imidazole (2014)
  • Author(s): K. Kamata, K. Sugahara, R. Ishimoto, S. Nojima, M. Okazaki, T. Matsumoto, N. Mizuno
  • Journal Title: Chem. Cat. Chem. Volume: 6 Issue: 8 Pages: 2327-2332
  • DOI: 10.1002/cctc.201402268
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Efficient and Selective N-Alkylation of Indoles with α,β-Unsaturated Compounds Catalyzed by a Monomeric Phosphate (2014)
  • Author(s): H. Sunaba, K. Kamata, N. Mizuno
  • Journal Title: Chem. Cat. Chem. Volume: 6 Issue: 8 Pages: 2333-2338
  • DOI: 10.1002/cctc.201402309
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Hydrosilylation of Various Multiple Bonds by a Simple Combined Catalyst of a Tungstate Monomer and Rhodium Acetate (2013)
  • Author(s): Shintaro Itagaki, Hanako Sunaba, Keigo Kamata, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: Chemistry Letters Volume: 42 Issue: 9 Pages: 980-982
  • DOI: 10.1246/cl.130338
  • NAID: 10031194313
  • Peer Reviewed
• [Journal Article] A Monovacant Lacunary Silicotungstate as an Efficient Heterogeneous Catalyst for Dehydration of Primary Amides to Nitriles (2013)
  • Author(s): Shintaro Itagaki, Keigo Kamata, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: Chem Cat Chem Volume: (印刷中) Issue: 7 Pages: 1725-1728
  • DOI: 10.1002/cctc.201300063
  • Peer Reviewed
• [Journal Article] Cubic Cesium Hydrogen Silicododecatungstates with Anisotropic Morphology and Polyoxometalate Vacancies Exhibiting Selective Water Sorption and Cation-Exchange Properties (2013)
  • Author(s): Y. Ogasawara, S. Uchida, T. Maruichi, R. Ishikawa, N. Shibata, Y. Ikuhara, N. Mizuno
  • Journal Title: Chemistry of Materials Volume: 25 Issue: 6 Pages: 905-911
  • DOI: 10.1021/cm3039448
  • Peer Reviewed
• [Journal Article] A Discrete Octahedrally Shaped [Ag6]4+ Cluster Encapsulated within Silicotungstate Ligands (2013)
  • Author(s): Y. Kikukawa, Y. Kuroda, K. Suzuki, M. Hihino K Yaiaguchi N Mizuno
  • Journal Title: Chem. Commun. Volume: 49 Pages: 376-378
  • Peer Reviewed
• [Journal Article] Rhodium Acetate/Base-Catalyzed N-Silylation of Indole Derivatives with Hydrosilanes (2012)
  • Author(s): Shintaro Itagaki, Keigo Kamata, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: Chemical Communivations Volume: 48 Issue: 74 Pages: 9269-9271
  • DOI: 10.1039/c2cc34381a
  • Peer Reviewed
• [Presentation] Selective Oxidation of Hydrocarbons with Aqueous Hydrogen Peroxide Catalyzed by Divanadium-substituted Polyoxometalates (2014)
  • Author(s): 水野 哲孝
  • Organizer: 248th ACS National Meeting
  • Place of Presentation: サンフランシスコ（米国）
  • Year and Date: 2014-08-11
  • Invited
• [Presentation] Highly Functionalized Polyoxometalate-Based Catalysts for Green Functional Group Transformations (2014)
  • Author(s): 水野 哲孝
  • Organizer: 41st International Conference on Coordination Chemistry
  • Place of Presentation: シンガポール（シンガポール）
  • Year and Date: 2014-07-23
  • Invited
• [Presentation] Polyoxometalate-based nano-structured catalysts for selective functional group transformations (2014)
  • Author(s): 水野 哲孝
  • Organizer: 3rd Frontiers in Metal Oxide Cluster Science
  • Place of Presentation: マフリエ（フランス）
  • Year and Date: 2014-07-12
  • Invited
• [Presentation] Innovative Basic Research Toward Creation of High-performance Battery", France-Japan Symposium on Advanced Materials for Energy Future (2014)
  • Author(s): 水野 哲孝
  • Organizer: Towards reliable, durable and safe materials for energy production and storage
  • Place of Presentation: 日本学術会議（東京）
  • Year and Date: 2014-07-01
  • Invited
• [Presentation] Innovative Basic Research Toward Creation of High-performance Battery (2014)
  • Author(s): 水野 哲孝
  • Organizer: Evonik Meets Science Japan 2014
  • Place of Presentation: ハイアットリージェンシーホテル（東京）
  • Year and Date: 2014-04-10
  • Invited
• [Presentation] Design and Synthesis, and catalysis of highly functionalized polyoxometalates (2014)
  • Author(s): Noritaka Mizuno
  • Organizer: 247th ACS National Meeting （口頭発表）
  • Place of Presentation: Dallas, TX, U. S. A.
• [Presentation] 分子性金属酸化物クラスターを基盤とした高機能触媒の開発 (2014)
  • Author(s): 水野哲孝
  • Organizer: 日本化学会第94春季年会 （受賞講演）
  • Place of Presentation: 名古屋, 名古屋大学
• [Presentation] Green Oxidative Synthesis of Primary Amides from Primary Alcohols, Primary Amines, or Alkylarenes Catalyzed by Manganese Oxides (2013)
  • Author(s): Noritaka Mizuno
  • Organizer: 10th Congress on Catalysis Applied to Fine Chemicals (CAFC10) （口頭発表）
  • Place of Presentation: Turku, Finland
• [Presentation] Design of Polyoxometalate-Based Molecular Catalysts for Bridging the Gap between Homogeneous and Heterogeneous Catalysis (2013)
  • Author(s): Noritaka Mizuno
  • Organizer: Frontiers at the interface of Homogeneous and Heterogeneous Catalysis Meeting
  • Place of Presentation: Annapolis, MD, U. S. A
  • Invited
• [Presentation] Design and Synthesis of Polyoxometalate-based Molecular Catalysts (2013)
  • Author(s): Noritaka Mizuno
  • Organizer: The 14th Japan-Korea Symposium on Catalysis （基調講演）
  • Place of Presentation: 名古屋, ウインクあいち
• [Presentation] Design of Highly Functionalized Polyoxometalate-Based Catalysts: From Molecular to Solid Catalysts (2013)
  • Author(s): Noritaka Mizuno
  • Organizer: The Sixteenth International Symposium of Relations between Homogeneous and Heterogeneous Catalysis (ISHHC-16) （基調（Keynote）講演）
  • Place of Presentation: 札幌, 北海道大学
• [Presentation] esign and Applications of Highly Functionalized Polyoxometalate-Based Materials (2013)
  • Author(s): Noritaka Mizuno
  • Organizer: 15th Asian Chemical Congress 2013
  • Place of Presentation: Sentosa Island, Singapore
  • Invited
• [Presentation] Synthesis of Unique Polyoxometalates Containing Discrete Ag Cluster and Their Catalysis for Hydrolytic Oxidation of Silanes (2013)
  • Author(s): Noritaka Mizuno
  • Organizer: EUROPACAT 2013 （口頭発表）
  • Place of Presentation: Lyon, France
• [Presentation] Design of Functionalized Polyoxometalate-based Nano-structured Catalysts (2012)
  • Author(s): N. Mizuno
  • Organizer: International Symposium on Advancing the Chemical Sciences (Invited)
  • Place of Presentation: Toronto, Canada
  • Year and Date: 2012-07-20