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

Photo-Driven Energy Storage System with Molecular

Research Project

Project/Area Number 07044148
Research Category

Grant-in-Aid for international Scientific Research

Allocation TypeSingle-year Grants
SectionJoint Research
Research InstitutionOsaka University

Principal Investigator

YANAGIDA Shozo  Osaka University, 工学部, 教授 (10029126)

Co-Investigator(Kenkyū-buntansha) FUJITA Etsuko  Brook Haven Notional Laboratory, 化学部門, 研究員
BRUNSCHWIG Bruce  Brook Haven Notional Laboratory, 化学部門, 研究員
CRUETZ Carol  Brook Haven Notional Laboratory, 化学部門・部門長, 主任研究員
SUTIN Norman  Brook Haven Notional Laboratory, 化学部門, 主任研究員
FUJIWARA Hiroaki  Osaka University, 工学部, 博士課程後期日本学術
HOSOKAWA Hiroji  Osaka University, 工学部, 博士課程後期日本学術
SUENOBU Tomoyoshi  Osaka University, 工学部, 助手 (90271030)
MURAKOSHI Kei  Osaka University, 工学部, 助手 (40241301)
ITOH Shinobu  Osaka University, 工学部, 助教授 (30184659)
WADA Yuji  Osaka University, 工学部, 助教授 (40182985)
FUKUZUMI Shun-ichi  Osaka University, 工学部, 教授 (40144430)
緒方 朋行  大阪大学, 工学部, 博士課程後期日本学術
Project Period (FY) 1995 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥8,100,000 (Direct Cost: ¥8,100,000)
Fiscal Year 1996: ¥3,300,000 (Direct Cost: ¥3,300,000)
Fiscal Year 1995: ¥4,800,000 (Direct Cost: ¥4,800,000)
Keywordscarbon dioxide / photochemistry / metal complex / artificial photosynthesis / linear aromatic compound / electron transfer / semiconductor / nanoparticles / 還元 / 半導体超微粒子 / 錯体
Research Abstract

Cobalt macrocycles mediate electron transfer in the photoreduction of CO_2 with p-terphenyl as the photosensitizer and a tertiary amine as the sacrificial electron donor. Mechanistic investigation was carried out using Co^1HMD (HMD=5,7,7,12,14,14-hexamethyl-1,4,8,11-tetrazacyclotetradeca-4,11-diene) by means of laser flash photolysis. The rate constant for electron transfer from the radical anion of p-terphenyl was determined. It was elucidated that not the electron transfer rate but coordination of CO_2 to the complex was controlled by the structure of the complex, which is reflected in the photocatalytic actibity of CO_2 reduction.
Nickel cyclam or other saturated 14-membered tetraazamacrocycles are used as catalysts instead of cobalt complexes, the above system does not produce CO.Instead a small amount of H_2 is fromed. Flash photolysis studies indicate that the Ni (I) species including NiL (CO_2)^+ form even in the absence of p-terphenyl upon irradiation at 313 nm under CO_2. Our studies indicate that Ni^<11>L^<2+> interacts with CO_2 in CH_3CN solution containing TEA (triethylamine) to from the Ni^<11>L (TEA) (CO_2)^<2+> adduct. NiL(CO_2)^+ seems to be produced by photoinduced electron transfer from the bound TEA.In addition to the nature of the Ni^<11>L (TEA) (CO_2)^<2+> adduct, differences between Co and Ni macrocycles (i.e., CO_2 binding constants, CO_2 binding rate constants, the pK_a of the hydrides, and redox properties) will be discussed.
Electron transfer rates for three coumarine dyes (Coumarins 343, D-1421, and D-126) adsorbed on TiO_2 and ZnO nanocrystallites were directly obtained from the ultra fast fluorescence dynamics, measured using the femtosecond upconversion technique. Observed ultra fast electron transfer injection should be due to not only the strong electronic couplong, but also large overlapping of the conduction band states of semiconductor and the donor states of excited molecules.

Report

(3 results)
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • Research Products

    (21 results)

All Other

All Publications (21 results)

  • [Publications] T.Ogata,Y.Yamamoto,Y.Wada,K.Murakoshi,M.Kusaba,N.Nakashima,A.Ishida,S.Takamuku,and S.Yanagida: "Phenazine-Photosensitized Reduction of CO_2 Mediated by a Cobalt-Cyclam Complex Through Electron and Hydrogen Transfer" J.Phys.Chem.99. 11916-11922 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Ogata,S.Yanagida,B.S.Brunschwig,and E.Fujita: "Mechanistic and Kinetic Studies of Cobalt Macrocycles in a Photochemical CO_2 Reduction System : Evidence of Co-CO_2 Adducts as Intermediates" J.Am.Chem.Soc.117. 6708-6716 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] E.Fujita,B.S.Brunschwig,D.Cabelli,M.M.Renner,L.R.Furenlid,T.Ogata,Y.Wada,S.Yanagida: "Photochemical Carbon Dioxide Reduction with Metal Complexes : Differences Between Cobalt And Nickel Macrocycles" Proceeding of Fourth International Conference on Carbon Dioxide Utilzation. (in press). (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] E.Fujita,B.S.Brunschwig,D.Cabelli,M.M.Renner,L.R.Furenlid,T.Ogata,Y.Wada,S.Yanagida: "Photochemical Carbon Dioxide Reduction with Cobalt and Nickel Macrocycles" Proceeding of Twelfth International Symposium on Photochemistry and Photophysics of Coordination Compound. (in press). (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Murakoshi,S.Yanagida,E.W.Castner,Jr.: "Ultrafast Electron-Transfer at Heterogeneous Interfaces : Coumarin Photosensitizers Adsorbed on TiO_2 and ZnO Nanoclusters in Aqueous and Methanol Solutions" Nanostructured Materials : Clusters,Composites,and Thin Films. (in press). (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Ogata, Y.Yamamoto, Y.Wada, K.Murakoshi, M,Kusaba, N.Nakashima, A.Ishida, S.Takamuku, and S.Yanagida: "Phenazine-Photosensitized Reduction of CO_2 Mediated by a Cobalt-Cyclam Complex Through Electron and Hydrogen Transfer" J.Phys.Chem.99. 11916-11922 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Ogata, S.Yanagida, B.S.Brunschwig, and E.Fujita: "Mechanistic and Kinetic Studies of Cobalt Macrocycles in a Photochemical CO_2 Reduction System : Evidence of Co-CO_2" J.Am.Chem.Soc.117. 6708-6716 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] E.Fujita, B.S.Brunschwig, D.Cabelli, M.M.Renner, L.R.Furenlid, T.Ogata, Y.Wada, S.Yanagida: "Photochemical Carbon Dioxide Reduction with Metal Complexes : Differences Between Cobalt And Nickel Macrocycles" Proceeding of Fourth International Conference on Carbon Dioxide Utilzation. (in press). (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] E.Fujita, B.S.Brunschwig, D.Cabelli, M.M.Renner, L.R.Furenlid, T.Ogata, Y.Wada, S.Yanagida: "Photochemical Carbon Dioxide Reduction with Cobalt and Nickel Macrocycles" Proceeding of Twelfth International Symposium on Photochemistry and Photophysics of Coordination Compound. (in press). (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Murakoshi, S.Yanagida, E.W.Castner, Jr.: "Ultrafast Electron-Transfer at Heterogeneous Interfaces : Coumarin Photosensitizers Adsorbed on TiO_2 and ZnO Nanoclusters in Aqueous and Methanol Solutions" Nanostructured Materials : Clusters, Composites, and Thin Films. (in press). (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Ogata,Y.Yamamoto,Y.Wada,K.Murakoshi,M.Kusaba,N.Nakashima,A.Ishida,S.Takamuku,and S.Yanagida: "Phenazine-Photosensitized Reduction of CO_2 Mediated by a Cobalt-Cyclam Complex Through Electron and Hydrogen Transfer" J.Phys.Chem.99. 11916-11922 (1995)

    • Related Report
      1996 Annual Research Report
  • [Publications] T.Ogata,S.Yanagida,B.S.Brunschwing,and E.Fujita: "Mechanistic and Kinetic Studies of Cobalt Macrocycles in a Photochemical CO_2 Reduction System:Evidence of Co-CO_2 Adducts as Intermediates" J.Am.Chem.Soc.117. 6708-6716 (1995)

    • Related Report
      1996 Annual Research Report
  • [Publications] E.Fujita,B.S.Brunschwig,D.Cabelli,M.M.Renner,L.R.Furenlid,T.Ogata,Y.Wada,S.Yanagida: "Photochemical Carbon Dioxide Reduction with Metal Complexes:Differences Between Cobalt And Nickel Macrocycles" Proceeding of Fourth International Conference on Carbon Dioxide Utilzation. (in press). (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] E.Fujita,B.S.Brunschwig,D.Cabelli,M.M.Renner,L.R.Furenlid,T.Ogara,Y.Wada,S.Yanagida: "Photochemical Carbon Dioxide Reduction with Cobalt and Nickel Macrocycles" Proceeding of Twelfth International Symposium on Photochemistry and Photophysics of Coordination Compound. (in press). (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] K.Murakoshi,S.Yanagida,E.W.Castner,Jr.: "Ultrafast Electron-Transfer at Heterogeneous Interfaces:Coumarin Photosensitizers Adsorbed on TiO_2 and ZnO Nanoclusters in Aqueous and Methanol Solutions" Nanostructured Materials:Clusters,Composites,and Thin Films. (in press). (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] T.Ogata ; Yoshie,Y.Wada,K.Murakoshi,S.Yanagida 他: "Phenazine-Photosensitized Reduction of CO2 Mediated by a Cobalt-Cyclam Complex Through Electron and Hydrogen Transfer" J.Phys.Chem.99. 11916-11922 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] T.Ogata,S.Yanagida,B.S.Brunschwig,E.Fujita: "Mechanistic and Kinetic Studies of Cobalt Macrocycles in a Photochemical CO2 Reduction System : Evidence of Co-CO2 Adducts as Intermediates" J.Am.Chem.Soc.117. 6708-6716 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] S.Yanagida,T.Ogata,H.Hosokawa,Y.Wada 他: "Semiconductor Photocatalysis : Size Control of Surface-Capped CdS Nanocrystallites and the Quantum Size Effect in Their Photocatalysis" Bull.Chem.Soc.Jpn.68. 752-758 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] S.Yanagida,Yuji Wada 他: "Semiconductor Photocatalysis : ZnS-Nanocrystallite-Catalyzed Photooxidation of Organic Compounds" Bull.Chem.Soc.Jpn.68. 1811-1823 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 和田 雄二、柳田 祥三: "有機溶媒中の金属硫化物超微結晶の光触媒反応:量子箱光触媒作用" 表面科学. 16. 180-187 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 柳田 祥三、緒方 朋行: "人工光合成:分子太陽電池を用いる二酸化炭素の光還元・固定" 化学と生物. 33. 342-344 (1995)

    • Related Report
      1995 Annual Research Report

URL: 

Published: 1995-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi