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Zeolite photochemistry : Investigation of cation-π interaction and diffusion of guest species

Research Project

Project/Area Number 14550796
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 工業物理化学
Research InstitutionGunma National College of Technology

Principal Investigator

HASHIMOTO Shuichi  Gunma College of Technology, Chemistry Dept., Professor, 一般教科(自然科学系), 教授 (70208445)

Project Period (FY) 2002 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 2003: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2002: ¥2,800,000 (Direct Cost: ¥2,800,000)
Keywordszeolite / rare earth / fluorescence / photochemistry / aromatics / energy transfer / diffusion / 吸着 / 結晶 / 希土類イオン / 芳香族分子 / 発光 / 時間分解分光
Research Abstract

1. A kinetic study on energy transfer between guest aromatic species and rare earth charge-compensating cations within zeolites :
The real-time observation is made of energy transfer (ET) between guest aromatic species, benzophenone and naphthalene, and a rare-earth charge compensating cation, Tb^<3+> within a faujasite zeolite Y by the measurement of a time-dependent rise and decay of emission from the ^5D_4 excited-state of Tb^<3+> on excitation of the guest molecules with a pulsed-laser light. Confinement of the guest species within the cages leads to a greatly enhanced emission intensity relative to solution systems, thus facilitating the ET by enforcing the formation of excited-state complexes. Besides, the kinetic behavior of the emission reveals that while benzophenone molecules are immobilized at the protonic sites within the cages, naphthalene molecules are still mobile leading to a remarkable observation of the loading-dependent rise and decay of the Tb^<3+> emission. Consiste … More nt with the assumption of the excited-state complex, a direct excitation of the absorption band of ^7F_6→^5D_4 band (488 nm) of Tb^<3+> results in a single-exponential emission decay with a lifetime of 2.4 ms both in the absence and in the presence of benzophenone or naphthalene.
2. Visual and spectroscopic demonstration of intercrystalline migration and resultant photochemical reactions of aromatic molecules adsorbed in zeolites :
We applied a fluorescence microscopic method to investigate the intercrystalline migration of aromatic molecules adsorbed in faujasite zeolites. Photophysical processes such as intersystem crossing and energy transfer assisted by particular charge compensating cations, and photochemical reactions such as charge transfer (CT) and triplet-triplet energy transfer between guest species incorporated in the zeolites were exploited as indicator reactions to afford luminescence color characteristic to an individual zeolite particle. Two types of migration mechanism were evidenced assisted by sample heating at temperatures between 60 and 120℃ : a through space diffusional transfer mode between separated zeolite crystals and a molecular injection process from a loaded crystal to another unloaded crystal, both in contact. A preferential direction of guest migration was found to exist for a few cases : for instance, aromatics such as naphthalene, phenanthrene and chrysene migrate from sodium form of zeolite X (Na^+-X) to thallium-exchanged zeolite X (Tl^+-X). On the other hand, the migration-assisted formation of CT complexes between electron-donating arenes such as phenanthrene and chrysene, and electron-accepting 1,2,4,5-tetracyanobenzene, both incorporated into separate zeolite Na^+-X crystals, takes place as a result of the migration of the donors. Less

Report

(3 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • Research Products

    (17 results)

All Other

All Publications (17 results)

  • [Publications] M.Kojima, M.Nakajoh, C.Matsubara, S.Hashimoto: "Photooxygenation of aromatic alkenes in zeolite nanocavities"J.Chem.Soc.Perkin 2. 1894-1901 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Hashimoto, S.Kirikae, S.Tobita: "A kinetic study on energy transfer between guest aromatic species and rare earth charge-compensating cations within zeolites"Phys.Chem.Chem.Phys.. 4. 5856-5862 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Hashimoto: "Visual and spectroscopic demonstration of intercrystalline migration and resultant photo chemical reactions of aromatic molecules"J.Phys.Chem.B. 107. 9763-9773 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Hashimoto: "Fluorescence microscopy investigation on the manipulation of guest species in zeolites"Res.Chem.Intermed.. 30(in press). (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hashimoto, S., Hagiri, M., Barzykin A.V.: "Triplet-triplet energy transfer as a tool for probing molecular diffusivity within zeolites"J.Phys.Chem.B. 106-4. 844-852 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hashimoto, S., Kirikae, S., Tobita, S.: "A kinetic study on energy transfer between guest aromatic species and rare earth charge-compensating cations within zeolites"Phys.Chem.Chem.Phys.. 4-23. 5856-5862 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Kojima, M., Nakajoh, M., Matsubara, C., Hashimoto, S.: "Photooxygenation of Aromatic Alkenes in Zeolite Nanocavities"J.Chem.Soc. Perkin Trans.2. 1894-1901 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hashimoto, S.: "Zeolite Photochemistry : Impact of Zeolites on Photochemistry and Feedback from Photochemistry to Zeolite Science"J.Photochem.Photobiol., C : Photochemistry Reviews.. 4-1. 19-49 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hashimoto, S., Kiuchi, J.: "Visual and spectroscopic demonstration of intercrystalline migration and resultant photochemical reactions of aromatic molecules adsorbed in zeolites"J.Phys.Chem.B. 107-36. 9763-9773 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hashimoto, S.: "Fluorescence microscopy investigation on the manipulation of guest species in zeolites"Res.Chem.Intermed.. 30-2. 163-179 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Alvaro, M., Ferrer, B., Garcia, H., Hashimoto, S, Hiratsuka, M., Asahi, T., Masuhara, H.: "Photochemistry of Charge-Transfer Complexes in a Viologen Periodic Mesoporous Organosilica From Femtosecond to Minutes Time Evolution"ChemPhysChem. 5(in press). (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Hashimoto: "Zeolite Photochemistry : Impact of Zeolites on Photochemistry and Feedback from Photochemistry to Zeolite Science"J.Photochem.Photobiol.C : Photochem.Reviews. 4・1. 19-49 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.Hashimoto, J.Kiuchi: "Visual and spectroscopic demonstration of intercrystalline migration and resultant photochemical reactions of aromatic molecules adsorbed in zeolites"J.Phys.Chem.B. 107・36. 9763-9773 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.Hashimoto: "Fluorescence microscopy investigation on the manipulation of guest species in zeolites"Res.Chem.Intermed.. 30(in press). (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] M.Kojima, M.Nakajoh, C.Matsubara, S.Hashimoto: "Photooxygenation of aromatic alkenes in zeolite nanocavities"J. Chem. Soc. Perkin 2. 1894-1901 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] S.Hashimoto, S.Kirikae, S.Tobita: "A kinetic study on energy transfer between guest aromatic species and rare earth charge-compensating cations within zeolites"Phys. Chem. Chem. Phys.. 4・23. 5856-5862 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] S.Hashimoto: "Zeolite photochemistry : Impact of zeolites on photochemistry and feed back from photochemistry to zeolite science"J. Photochem. Photobiol. C : Photochem Reviews. 4(in press). (2003)

    • Related Report
      2002 Annual Research Report

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Published: 2002-04-01   Modified: 2016-04-21  

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