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Dynamics of transition-metal complex in supercritical CO_2 as studied by NMR

Research Project

Project/Area Number 11440176
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Physical chemistry
Research InstitutionOsaka University

Principal Investigator

EGUCHI Taro  Graduate School of Science, Osaka University, Professor, 大学院・理学研究科, 教授 (50107083)

Co-Investigator(Kenkyū-buntansha) NAKAYAMA Hirokazu  Kobe Pharmaceutical University, Associate Professor, 助教授 (40189080)
UEDA Takahiro  Graduate School of Science, Osaka University, Research Associate, 大学院・理学研究科, 助手 (70294155)
MIYAKUBO Keisuke  Graduate School of Science, Osaka University, Research Associate, 大学院・理学研究科, 助手 (70263340)
Project Period (FY) 1999 – 2001
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥15,400,000 (Direct Cost: ¥15,400,000)
Fiscal Year 2001: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 2000: ¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 1999: ¥10,900,000 (Direct Cost: ¥10,900,000)
KeywordsSuper-critical fluid / Xenon / Carbon dioxide / High pressure NMR / Porous materials / Molecular sieves / Catalysis / Dynamics / ポリマー / 遷移金属錯体
Research Abstract

In 1999 we designed and built a new high-pressure NMR probe which can be used in a heterogeneous system under the supercritical condition of CO_2 (T_c = 31.0℃, P_c = 72.9atm). In situ NMR measurements can be performed in a temperature range between - 70 ℃ and + 150 ℃ , and in a pressure range below 20 MPa by using this probe.
^<129>Xe NMR was recorded on a Bruker MSL-200 spectrometer to investigate physico-chemical properties of micropores and/or mesopores in various porous systems. The critical parameters of Xe are Tc = 289.8 K, Pc = 5.8 MPa, and ρ_c = 1.15 gcm^<-3>.
At the first stage, we studied the free volumes in polymers which can adsorb Xe very weakly. The size of the micropore in each polymer was determined by ^<129>Xe NMR and was compared with the result of the positron annihilation experiment.
In the next stage, we applied the first high-pressure ^<129>Xe NMR to the meoporous silica, FSM-16. Three types of samples were used, which have different diameters (d) of the mesopore, being d = 1.9, 2.7, and 4.1 nm. It was found that there are two inequivalent Xe inside the mesopore with d = 1.9 nm. On the other hand, a single resonance line was observed in the mesopore with d = 4.1 nm. It was concluded that at least a diameter of d = 2.7 nm is necessary to detect the evidence of the critical phenomenon in the mesopore.
Finally we are now studying adsorption properties of molecular sieves 5A and 13X by using high-pressure ^<129>Xe NMR. It follows that not only water molecules inside the micropores but also the particle sizes affect Xe adsorption into these molecular sieves.

Report

(4 results)
  • 2001 Annual Research Report   Final Research Report Summary
  • 2000 Annual Research Report
  • 1999 Annual Research Report
  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] 永阪文惣, 江口太郎: "簡易型高圧NMRプローブの試作-"大阪大学低温センターだより. No.107. 19-23 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Bunsow Nagasaka: "Positron annihilation and ^<129>Xe NMR studies of free volume in polymers"Radiation Physics and Chemistry. 58. 581-585 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Bunsow Nagasaka: "High-pressure ^<129>Xe NMR study of supercritical senon interacting with polymers"Chemical Physics Letters. 340. 473-478 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 永阪文惣, 江口太郎: "「不思議な超臨界流体をNMRで観る」"化学. 56(9). 25-27 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 中山尋量, 尾身洋典: "特異な条件下でのガスハイドレートの形成-"高圧力の科学と技術. 12(1). 10-15 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Bunsow Nagasaka, Taro Eguchi, Hirokazu Nakayama, Nobuo Nakamura, and Yasuo Ito: "Positron annihilation and ^<129>Xe NMR studies of free volume in polymers"Radiation Physics and Chemistry. 58. 581-585 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Bunsow Nagasaka, Hironori Omi, Taro Eguchi, Hirokazu Nakayama, and Nobuo Nakamura: "High-pressure ^<129>Xe NMR study of supercritical xenon interacting with polymers"Chemical Physics Letters. 340. 473-478 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Bunsow Nagasaka: "High-Pressure ^<129>Xe NMR Study of Supercritical Xenon Interacting with Polymers"Chemical Phy sics Letters. 340. 473-478 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 中山尋量: "特異な条件下でのガスハイドレートの形成"高圧力の科学と技術. 12・1. 10-15 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Bunsow Nagasaka: "Positron Annihilation and ^<129>Xe NMR Studies of Free Volume in Polymers"Radiation Physics and Chemistry. 58. 581-585 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Bunsow Nagasaka: "High-Pressure ^<129>Xe NMR Study of Supercritical Xenon Interacting with Polymers"Chemical Physics Letters. (印刷中). (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] 永阪文惣: "簡易型高圧NMRプローブの試作"大阪大学低温センターだより. 107. 19-23 (1999)

    • Related Report
      1999 Annual Research Report

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Published: 1999-04-01   Modified: 2016-04-21  

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