• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Energy-Controlled Spaces at the Single-Molecule Photo-Hydrogen-Evolving Devices

Research Project

Project/Area Number 16074216
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionKyushu University

Principal Investigator

SAKAI Ken  Kyushu University, Faculty of Science, Professor (30235105)

Co-Investigator(Kenkyū-buntansha) MASAOKA Shigeyuki  KYUSHU UNIVERSITY, Faculty of Science, Assistant Professor (20404048)
Project Period (FY) 2004 – 2006
Project Status Completed (Fiscal Year 2007)
Budget Amount *help
¥7,700,000 (Direct Cost: ¥7,700,000)
Fiscal Year 2006: ¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 2005: ¥2,900,000 (Direct Cost: ¥2,900,000)
Fiscal Year 2004: ¥2,100,000 (Direct Cost: ¥2,100,000)
KeywordsHydrogen evolution / Metal complexes / Photocatalysts / Energy / 光水素発生触媒 / 白金錯体 / 水素エネルギー / ルテニウム錯体 / 光増感 / 電荷分離 / 分子デバイス / 多核金属錯体 / 太陽光エネルギー / ビオローゲン / 人工光合成 / ナノデバイス
Research Abstract

Great attention has been paid to the studies on the photocatalytic systems promoting the solar-light-induced splitting of water into H_2 and 1/2O_2, because water and sunlight are abundant and such systems are free of the CO_2 emission. Since the original discovery in the H_2-evolving activities of amidate-bridged Pt(II)_2 dimers having a relatively strong metal-metal interaction, considerable efforts have been made to develop the 'photo-hydrogen-evolving (PHE)' molecular devices (MDs) that are made up of photosensitizing Ru(bpy)_3^<2+> derivatives and H_2-evolving Pt(II) catalysts. Such PHEMDs are expected to serve as an efficient 'photocatalyst'towards the visible-light-induced reduction of H_2_O by EDTA into H_2. As a result, we discovered that one particular molecular device consisting of a [Ru(bpy)_2(5-amino-phen)]^<2+> unit and a PtCl_2(bpy) unit evolves H_2 in the presence of EDTA under the visible light illumination.
In this project, several other related compounds have also been prepared and evaluated to better understand the factors affecting the PHE activities of such PHEMDs These studies suggested the following key factors: (i) destabilization of the HOMO corresponding to the filled Pt(II) dz^2 orbital enhances the PHE activity; (ii) steric hindrances around the axial site of the square-planar Pt(II) coordination sphere lower the PHE activity; (iii) an appropriate aromaticity is needed to enhance the intramolecular electron transfer processes; (iv) EDTA forms an adduct with a PHEMD before undertaking the H_2 generation; (v) the H_2 formation undergoes via a bimolecular process of the PHEMD. In addition to these results, the electrochemical studies, stopped flow experiments looking at the reactions between the Pt(II) complexes and a radical cation generated from methylviologen, and DFT MO investigations have been examined.

Report

(3 results)
  • 2007 Final Research Report Summary
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • Research Products

    (21 results)

All 2007 2006 2005 2004

All Journal Article (20 results) (of which Peer Reviewed: 4 results) Presentation (1 results)

  • [Journal Article] Syntheses, Characterization, and Photo-Hydrogen-Evolving Properties of Tris (2, 2' - bipyridine)ruthenium(II) Derivatives Tethered to a cis-Pt(II)C12 Unit : Insights into the Structure-Activity Relationship2007

    • Author(s)
      Hironobu Ozawa, Yuki Yokoyama, Masa-aki Haga, Ken Sakai
    • Journal Title

      Dalton Trans.

      Pages: 1197-1206

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Homogeneous catalysis of platinum(II) complexes in photochemical hydrogen production from water2007

    • Author(s)
      Ken Sakai, Hironobu Ozawa
    • Journal Title

      Coord. Chem. Rev. 251

      Pages: 2753-2766

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] An Effect of Structural Modification in the Photo-hydrogen-evoluting RuIIPtII Dimers2007

    • Author(s)
      Hironobu Ozawa, Ken Sakai
    • Journal Title

      Chem. Lett. 36

      Pages: 920-921

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Syntheses, Characterization, and Photo-Hydrogen-Evolving Properties of Tris(2,2'-bipyridine)ruthenium(II) Derivatives Tethered to a cis-Pt(II)C12 Unit : Insights into the Structure-Activity Relationship2007

    • Author(s)
      Hironobu Ozawa, Yuki Yokoyama, Masa-aki Haga, Ken Sakai
    • Journal Title

      Dalton Trans.

      Pages: 1197-1206

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] A Photo-Hydrogen-Evolving Molecular Device Driving Visible-Light-Induced EDTA-Reduction of Water into Molecular Hydrogen2006

    • Author(s)
      Hironobu Ozawa, Masa-aki Haga, Ken Sakai
    • Journal Title

      J. Am. Chem. Soc. 128

      Pages: 4926-4927

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] A Photo-Hydrogen-Evolving Molecular Device Driving Visible-Light-Induced EDTA-Reduction of Water into Molecular Hydrogen2006

    • Author(s)
      Hironobu Ozawa, Masa-aki Haga, Ken Sakai
    • Journal Title

      J. Am. Chem. Soc.

      Pages: 4926-4927

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Tetrakis(2-thiopydridone) platinum(II) chloride2005

    • Author(s)
      Mina Mizota, Yoshimi Yokoyama, Ken Sakai
    • Journal Title

      Acta Crystallogr. E61

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Dinuclear Mn(II), Ni(II), and Zn(II) Complexes Bridged by Bis (p-nitrophenyl) Phosphate Ion2005

    • Author(s)
      Shiraishi et al.
    • Journal Title

      Bull.Chem.Soc.Jpn. 78

      Pages: 1072-1076

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Construction of Pseudo-Heterochiral and -Homochiral Di-μ-oxotitanium(Schiff base) Dimers and Enantioselective Epoxidation Using Aqueous Hydrogen Peroxide2005

    • Author(s)
      Kazuhiro Matsumoto, Yuji Sawada, Bunnai Saito, Ken Sakai, Tsutomu Katsuki
    • Journal Title

      Angew.Chem.Int.Ed. 44

      Pages: 4935-4939

    • Related Report
      2005 Annual Research Report
  • [Journal Article] (2,2' -Bipyridine)chloro(4' -tolyl-2,2' : 6',2'' -terpyridine)iridium(III) bis(hexafluorophosphate) acetonitrile disolvate2005

    • Author(s)
      Tomona Yutaka Shinya Obara, Masa-aki Haga, Yoshimi Yokoyama, Ken Sakai
    • Journal Title

      Acta Crystallogr. E61

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Syntheses and Properties of Emissive Iridium(III) Complexes with Tridentate Benzimidazole Derivatives2005

    • Author(s)
      Yutaka et al.
    • Journal Title

      Inorg.Chem. 44

      Pages: 4737-4746

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Total Synthesis of Epoxyquinols A, B, and C and Epoxytwinol A and the Reactivity of a 2H-Pyran Derivative as the Diene Component in the Diels-Alder Reaction2005

    • Author(s)
      Shoji et al.
    • Journal Title

      J.Org.Chem. 70

      Pages: 79-91

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Total Synthesis of Epoxyquinols A, B, and C and Epoxytwinol A and the Reactivity of a 2H-Pyran Derivative as the Diene Component in the Diels-Alder Reaction2005

    • Author(s)
      M.Shoji, H.Imai, M.Mukaida, K.Sakai, H.Kakeya, H.Osada, Y.Hayashi
    • Journal Title

      J.Org.Chem. 70

      Pages: 79-91

    • Related Report
      2004 Annual Research Report
  • [Journal Article] The First Bent for the Hydroxo-Bridged cis-Diammineplatinum(II) Dimer :[Pt_2(NH_3)_4(μ-OH)_2](ClO_4)_22004

    • Author(s)
      Ken Sakai, Yosuke Konno, Noboru Takayama, Satoru Takahashi
    • Journal Title

      Acta Crystallographica B60

      Pages: 255-262

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Di-μ-aminopyridinato-bis[(2,2'-bipyridine)platinum(II)] dinitrate tetrahydrate in a head-to-tail isomerism2004

    • Author(s)
      Mina Mizota, Ken Sokai
    • Journal Title

      Acta Crystallographica E60

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Di-μ-pivalamidate-κ^4N,O-bis[(sulfato)(2,2'-bipyridine-κ^2N, N')-platinum(III)] tetrahydrate in a head-to-tail isomerism2004

    • Author(s)
      Kazuo Yokokawa, Ken Sakai
    • Journal Title

      Acta Crystallographica C60

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Bis[μ-3-(N'-methyl-4,4'-bipyridinium-1-yl)propionamidato]bis[cis-diammine platinum(II)] hexaperchlorate dihydrate in a head-to-tail isomerism2004

    • Author(s)
      Ken Sakai, Yoshimi Yokoyama, Hideki Hama, Kaoru Kato, Yoshie Ikuta, Taro Tsubomura, Tomoaki Tanase
    • Journal Title

      Acta Crystallographica E60

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Linear, Redox-Active Pt_6 and Pt_2Pd_2Pt_2 Clusters2004

    • Author(s)
      Eri Goto, Rowshan A.Begum, Shuzhong Zhan, Tomoaki Tanase Katsumi Tanigaki, Ken Sakai
    • Journal Title

      Angew.Chem.Int.Ed. 43

      Pages: 5029-5032

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Electron-Rich Diplatinum(0) Metallocryptate Promoting Novel Successive Encasulation of Acidic Hydrides2004

    • Author(s)
      Eri Goto, Miho Usuki, Hiroe Takenaka, Ken Sakai, Tomoaki Tanase
    • Journal Title

      Organometallics 23

      Pages: 6042-6051

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Reactive Rigid-Rod Organometallic Polymers Involving Linear Triplatinum Units Connected by p-Conjugated Bisisocyanides2004

    • Author(s)
      T.Tanase, E.Goto, R.A.Begum, M.Hamaguchi, S.g Zhan, M.Iida, K.Sakai
    • Journal Title

      Organometallics 23

      Pages: 5975-5988

    • Related Report
      2004 Annual Research Report
  • [Presentation] Photo-hydrogen-evolving molecular devices consisting of Ru(II) and Pt(II) centers2007

    • Author(s)
      Ken Sakai
    • Organizer
      The 17th International Symposium on the Photochemistry and Photophysics of Coordination Compounds (ISPPCC)
    • Place of Presentation
      Trinity College, Dublin, Ireland
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary

URL: 

Published: 2004-04-01   Modified: 2018-03-28  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi