Catalyst Development by Synergistic Effects of Complex Metal Oxide Clusters

• Project/Area Number: 26708009
• Research Category: Grant-in-Aid for Young Scientists (A)
• Allocation Type: Partial Multi-year Fund
• Research Field: Functional solid state chemistry
• Research Institution: The University of Tokyo
• Principal Investigator: SUZUKI Kosuke 東京大学, 工学(系)研究科(研究院), 助教 (40595667)
• Project Period (FY): 2014-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥19,890,000 (Direct Cost: ¥15,300,000、Indirect Cost: ¥4,590,000); Fiscal Year 2016: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000); Fiscal Year 2015: ¥5,720,000 (Direct Cost: ¥4,400,000、Indirect Cost: ¥1,320,000); Fiscal Year 2014: ¥11,180,000 (Direct Cost: ¥8,600,000、Indirect Cost: ¥2,580,000)
• Keywords: 触媒 / ポリオキソメタレート / 金属多核構造 / 光触媒 / ナノ材料 / 構造・機能材料 / 超分子化学

Outline of Final Research Achievements

The visible-light-responsive molecular catalysts were successfully developed by utilizing synergistic effects of molecular metal oxide clusters with multinuclear metal cores or organic molecules. These catalysts showed the intramolecular charge transfer properties by irradiation with visible light. In addition, they showed selective, efficient photocatalysis for the oxidation reactions of amines and sulfides using molecular oxygen as the oxidant as well as the reductive deoxygenation reactions of sulfoxides and pyridine N-oxides using alcohols as the reducing agents.

Research Products

• [Journal Article] Phosphovanadomolybdic acid catalyzed direct C-H trifluoromethylation of (hetero)arenes using NaSO2CF3 as the CF3 source and O2 as the terminal oxidant (2017)
  • Author(s): Li, C.; Suzuki, K.; Yamaguchi, K.; Mizuno, N.
  • Journal Title: New J. Chem. Volume: 41 Issue: 4 Pages: 1417-1420
  • DOI: 10.1039/c6nj03654f
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis and Disassembly/Reassembly of Giant Ring-Shaped Polyoxotungstate Oligomers (2016)
  • Author(s): Takuo Minato, Kosuke Suzuki, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: Angewandte Chemie International Edition Volume: 55 Issue: 33 Pages: 9630-9633
  • DOI: 10.1002/anie.201604094
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Hexanuclear Tin(II) and Mixed Valence Tin(II,IV) Oxide Clusters within Polyoxometalates (2016)
  • Author(s): Kosuke Suzuki, Takumi Hanaya, Rinta Sato, Takuo Minato, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: Chemical Communication Volume: 52 Issue: 70 Pages: 10688-10691
  • DOI: 10.1039/c6cc05284c
  • Peer Reviewed
• [Journal Article] Selective Deoxygenation of Pyridine N-Oxides through Photoredox Catalysis of a Dilacunary Silicotungstate (2016)
  • Author(s): J. Jeong, K. Suzuki, M. Hibino, K. Yamaguchi, N. Mizuno
  • Journal Title: ChemistrySelect Volume: 1 Issue: 15 Pages: 5042-5048
  • DOI: 10.1002/slct.201601146
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Photoredox catalysis for oxygenation/deoxygenation between sulfides and sulfoxides by visible-light-responsive polyoxometalates (2016)
  • Author(s): K. Suzuki, J. Jeong, K. Yamaguchi, N. Mizuno
  • Journal Title: New J. Chem. Volume: 40 Issue: 2 Pages: 1014-1021
  • DOI: 10.1039/c5nj01045d
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Sequential Synthesis of 3d-3d’-4f Heterometallic Heptanuclear Clusters in between Lacunary Polyoxometalates (2016)
  • Author(s): R. Sato, K. Suzuki, T. Minato, K. Yamaguchi, N. Mizuno
  • Journal Title: Inorg. Chem. Volume: 55 Issue: 5 Pages: 2023-2029
  • DOI: 10.1021/acs.inorgchem.5b02358
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Water- and Temperature-Triggered Reversible Structural Transformation of Tetranuclear Cobalt(II) Cores Sandwiched by Polyoxometalates (2016)
  • Author(s): Yosuke Kuriyama, Yuji Kikukawa, Kosuke Suzuki, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: Chemistry A European Journal Volume: ２２ Issue: 12 Pages: 3962-3966
  • DOI: 10.1002/chem.201600139
  • Peer Reviewed
• [Journal Article] A Cascade Approach to Hetero-Pentanuclear Manganese-Oxide Clusters in Polyoxometalates and Their Single-Molecule Magnet Properties (2015)
  • Author(s): Kosuke Suzuki, Rinta Sato, Takuo Minato, Masahiro Shinoe, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: Dalton Transaction Volume: 44 Issue: 32 Pages: 14220-14226
  • DOI: 10.1039/c5dt01363a
  • Peer Reviewed
• [Journal Article] Visible-Light-Responsive Multielectron Redox Catalysis of Lacunary Polyoxometalates Induced by Substrate Coordination to Their Lacuna (2015)
  • Author(s): K. Suzuki, J. Jeong, K. Yamaguchi, N. Mizuno
  • Journal Title: Chem. Asian J. Volume: 10 Issue: 1 Pages: 144-148
  • DOI: 10.1002/asia.201403072
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Field-Induced Slow Magnetic Relaxation of Octahedrally Coordinated Mononuclear Fe(III)-, Co(II)-, and Mn(III)-Containing Polyoxometalates (2015)
  • Author(s): R. Sato, K. Suzuki, T. Minato, M. Shinoe, K. Yamaguchi, N. Mizuno
  • Journal Title: Chem. Commun. Volume: 51 Issue: 19 Pages: 4081-4084
  • DOI: 10.1039/c4cc09435b
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Visible-Light-Induced Photoredox Catalysis with a Tetracerium-Containing Silicotungstate (2014)
  • Author(s): K. Suzuki, F. Tang, Y. Kikukawa, K. Yamaguchi, N. Mizuno
  • Journal Title: Angew. Chem. Int. Ed. Volume: 53 Issue: 21 Pages: 5356-5360
  • DOI: 10.1002/anie.201403215
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis of α-Dawson-Type Silicotungstate [Si2W18O62]8- and Protonation and Deprotonation Inside the Aperture via Intramolecular Hydrogen Bonds (2014)
  • Author(s): T. Minato, K. Suzuki, K. Kamata, N. Mizuno
  • Journal Title: Chem. Eur. J. Volume: 20 Issue: 20 Pages: 5946-5952
  • DOI: 10.1002/chem.201400390
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Hydrogen Evolution Using the Visible-Light-Induced Metal-to-Polyoxometalate Multiple Electron Transfer (2014)
  • Author(s): K. Suzuki, F. Tang, Y. Kikukawa, K. Yamaguchi, N. Mizuno
  • Journal Title: Chem. Lett. Volume: 43 Issue: 9 Pages: 1429-1431
  • DOI: 10.1246/cl.140450
  • NAID: 130004427164
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] Phosphovanadomolybdic Acid Catalyzed Trifluoromethylation of Arenes (2017)
  • Author(s): Chifeng Li, Kosuke Suzuki, Kazuya Yamaguchi, Noritaka Mizuno
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶応義塾大学（神奈川県・横浜市）
  • Year and Date: 2017-03-16
• [Presentation] Sequential Synthesis of Heterometallic Nonanuclear Clusters by Utilizing Lacunary Polyoxometalates (2017)
  • Author(s): Takuo Minato, Yusuke Ohata, Rinta Sato, Kosuke Suzuki, Kazuya Yamaguchi, Noritaka Mizuno
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶応義塾大学（神奈川県・横浜市）
  • Year and Date: 2017-03-16
• [Presentation] 二欠損型シリコタングステート可視光応答型光触媒によるピリジンN-オキシドの選択的脱酸素反応 (2017)
  • Author(s): 鄭進宇，鈴木康介，山口和也，水野哲孝
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶応義塾大学（神奈川県・横浜市）
  • Year and Date: 2017-03-16
• [Presentation] p-ブロック元素を導入したシリコタングステートの合成と特性 (2017)
  • Author(s): 鈴木康介，花屋巧，佐藤林太，山口和也，水野哲孝
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶応義塾大学（神奈川県・横浜市）
  • Year and Date: 2017-03-16
• [Presentation] 金属多核構造を導入したリング状ホスホタングステートの合成 (2016)
  • Author(s): 米里健太郎，鈴木康介，山口和也，水野哲孝
  • Organizer: 第6回CSJ化学フェスタ2016
  • Place of Presentation: タワーホール船堀（東京都・江戸川区）
  • Year and Date: 2016-11-14
• [Presentation] 欠損型ポリオキソメタレートを用いた混合原子価スズ酸化物クラスターの合成と光触媒特性 (2016)
  • Author(s): 花屋巧，鈴木康介，佐藤林太，湊拓生，山口和也，水野哲孝
  • Organizer: 第6回CSJ化学フェスタ2016
  • Place of Presentation: タワーホール船堀（東京都・江戸川区）
  • Year and Date: 2016-11-14
• [Presentation] Aerobic Oxidative Trifluoromethylation of Aromatic Compounds Catalyzed by Vanadium-Containing Phosphomolybdic Acids (2016)
  • Author(s): 李赤峰，鈴木康介，山口和也，水野哲孝
  • Organizer: 第6回CSJ化学フェスタ2016
  • Place of Presentation: タワーホール船堀（東京都・江戸川区）
  • Year and Date: 2016-11-14
• [Presentation] 可視光応答型シリコタングステートを用いた有機硫黄化合物の選択的光酸化還元反応 (2016)
  • Author(s): 鈴木康介，鄭進宇，山口和也，水野哲孝
  • Organizer: 第118回触媒討論会
  • Place of Presentation: 岩手大学（岩手県・盛岡市）
  • Year and Date: 2016-09-21
• [Presentation] Syntheses and Single-Molecule Magnet Properties of Hetero-Multinuclear Manganese-Oxide Clusters Possessing Large Spin Ground State (2016)
  • Author(s): Takuo Minato, Yusuke Ohata, Kosuke Suzuki, Kazuya Yamaguchi, Noritaka Mizuno
  • Organizer: 錯体化学会第66回討論会
  • Place of Presentation: 福岡大学（福岡県・博多市）
  • Year and Date: 2016-09-10
• [Presentation] 混合原子価スズ酸化物を有するポリオキソメタレートの合成と光触媒特性 (2016)
  • Author(s): 花屋巧，鈴木康介，佐藤林太，湊拓生，山口和也，水野哲孝
  • Organizer: 錯体化学会第66回討論会
  • Place of Presentation: 福岡大学（福岡県・博多市）
  • Year and Date: 2016-09-10
• [Presentation] Visible-light-responsive photoredox catalysis of polyoxometalates (2016)
  • Author(s): Kosuke Suzuki, Kazuya Yamaguchi, Noritaka Mizuno
  • Organizer: International Symposium on Pure & Applied Chemistry 2016
  • Place of Presentation: Kuching (Malaysia)
  • Year and Date: 2016-08-17
  • Int'l Joint Research / Invited
• [Presentation] Stimuli-Responsive Reversible Structural Transformation of Multinuclear Metal Cores Sandwiched by Polyoxometalates (2016)
  • Author(s): Kosuke Suzuki, Kazuya Yamaguchi, Noritaka Mizuno
  • Organizer: 42nd International Conference on Coordination Chemistry (ICCC 2016)
  • Place of Presentation: Brest (France)
  • Year and Date: 2016-07-04
  • Int'l Joint Research
• [Presentation] Synthesis and Rearrangement of Ring-Shaped Manganese-Substituted Phosphotungstates (2016)
  • Author(s): Takuo Minato, Kosuke Suzuki, Kazuya Yamaguchi, Noritaka Mizuno
  • Organizer: 42nd International Conference on Coordination Chemistry (ICCC 2016)
  • Place of Presentation: Brest (France)
  • Year and Date: 2016-07-04
  • Int'l Joint Research
• [Presentation] 水および温度応答性コバルト多核構造を有するポリオキソメタレートの合成と可逆構造変換 (2016)
  • Author(s): 鈴木康介，栗山陽介，菊川雄司，山口和也，水野哲孝
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 京都府，京田辺市，同志社大学
  • Year and Date: 2016-03-24
• [Presentation] リング状Mn置換ホスホタングステートの合成とアニオン構造の再構築 (2016)
  • Author(s): 湊拓生，鈴木康介，山口和也，水野哲孝
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 京都府，京田辺市，同志社大学
  • Year and Date: 2016-03-24
• [Presentation] Visible-light-responsive photoredox catalysis of silicotungstates (2015)
  • Author(s): Kosuke Suzuki, Noritaka Mizuno
  • Organizer: Pacifichem 2015
  • Place of Presentation: ホノルル，アメリカ
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] Visible-light-responsive multielectron redox catalysis utilizing electron transfer from coordinated alcohols to lacunary polyoxometalates (2015)
  • Author(s): Jinu Jeong, Kosuke Suzuki, Kazuya Yamaguchi, Noritaka Mizuno
  • Organizer: Pacifichem 2015
  • Place of Presentation: ホノルル，アメリカ
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] Inorganic anionic cage [α-Si2W18O62]8– with reversible proton capturing inside the aperture via intramolecular hydrogen bonds (2015)
  • Author(s): Takuo Minato, Kosuke Suzuki, Keigo Kamata, Noritaka Mizuno
  • Organizer: Pacifichem 2015
  • Place of Presentation: ホノルル，アメリカ
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] 欠損型シリコタングステートを用いた可視光応答型酸化還元触媒反応 (2015)
  • Author(s): 鈴木康介，鄭進宇，山口和也，水野哲孝
  • Organizer: 第48回酸化反応討論会
  • Place of Presentation: 京都府，京都市，同志社大学
  • Year and Date: 2015-10-23
• [Presentation] 欠損型ポリオキソメタレートを用いた異種金属五核構造の逐次合成と単分子磁石特性 (2015)
  • Author(s): 湊拓生，鈴木康介，佐藤林太，篠江真広，山口和也，水野哲孝
  • Organizer: 錯体化学会第65回討論会
  • Place of Presentation: 奈良県，奈良市，奈良女子大学
  • Year and Date: 2015-09-21
• [Presentation] Visible-light-responsive multielectron redox catalysis of lacunary polyoxometalates utilizing their lacuna (2015)
  • Author(s): 鄭進宇，鈴木康介，山口和也，水野哲孝
  • Organizer: 錯体化学会第65回討論会
  • Place of Presentation: 奈良県，奈良市，奈良女子大学
  • Year and Date: 2015-09-21
• [Presentation] 金属酸化物クラスターを用いた触媒および高機能材料の開発 (2015)
  • Author(s): 鈴木康介
  • Organizer: 触媒学会若手会 第26回フレッシュマンゼミナール
  • Place of Presentation: 東京都，新宿区，早稲田大学
  • Year and Date: 2015-05-27
  • Invited
• [Presentation] 欠損型ポリオキソメタレートへの基質の配位による可視光応答型多電子酸化還元光触媒の開発 (2015)
  • Author(s): 鄭進宇，鈴木康介，山口和也，水野哲孝
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 千葉，日本大学
  • Year and Date: 2015-03-26
• [Presentation] 欠損型ポリオキソメタレートを用いた可視応答型多電子酸化還元触媒の開発 (2014)
  • Author(s): 鄭進宇，鈴木康介，山口和也，水野哲孝
  • Organizer: 第4回CSJ化学フェスタ2014
  • Place of Presentation: 東京，タワーホール船堀
  • Year and Date: 2014-10-16
• [Presentation] 欠損型ポリオキソメタレートアルコキサイドの合成 (2014)
  • Author(s): 湊拓生，鈴木康介，水野哲孝
  • Organizer: 第4回CSJ化学フェスタ2014
  • Place of Presentation: 東京，タワーホール船堀
  • Year and Date: 2014-10-16
• [Presentation] セリウム四核構造を導入したシリコタングステートの合成と可視光応答型酸化還元触媒特性 (2014)
  • Author(s): 鈴木康介，湯飛，菊川雄司，山口和也，水野哲孝
  • Organizer: 第114回触媒討論会
  • Place of Presentation: 広島，広島大学
  • Year and Date: 2014-09-25