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Mechanisms of Solid-Water Interfacial Reactions Involving Redox Reactions Studied by Laser Spectroscopy and Quantum Chemical Calculation

Research Project

Project/Area Number 17206098
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field Nuclear engineering
Research InstitutionThe University of Tokyo

Principal Investigator

TANAKA Satoru  The University of Tokyo, Graduate School of Engineering, Professor (10114547)

Co-Investigator(Kenkyū-buntansha) NAGASAKI Shinya  The University of Tokyo, Graduate School of Engineering, Professor (20240723)
TSUNEDA Takao  The University of Tokyo, Graduate School of Engineering, Associate Professor (20312994)
TORAISHI Takashi  Japan Atomic Energy Agency, Nuclear Science and Engineering Directorate, Postdoctoral Researsher (40376497)
KIMURA Takaumi  Japan Atomic Energy Agency, Nuclear Science and Engineering Directorate, Group Leader (20354897)
SAITO Takumi  The University of Tokyo, Graduate School of Engineering, Assistant Professor (90436543)
Project Period (FY) 2005 – 2007
Project Status Completed (Fiscal Year 2007)
Budget Amount *help
¥49,790,000 (Direct Cost: ¥38,300,000、Indirect Cost: ¥11,490,000)
Fiscal Year 2007: ¥10,530,000 (Direct Cost: ¥8,100,000、Indirect Cost: ¥2,430,000)
Fiscal Year 2006: ¥11,700,000 (Direct Cost: ¥9,000,000、Indirect Cost: ¥2,700,000)
Fiscal Year 2005: ¥27,560,000 (Direct Cost: ¥21,200,000、Indirect Cost: ¥6,360,000)
KeywordsLaser Spectroscopy / Quantum chemical calculation / Redox reactions / Solid / solution interface / Actinides / 電荷移動 / 配位子架橋 / ウラン / 密度汎関数理論 / EXAFS / 錯体形成 / 鉄 / アクチニド / 放射性廃棄物 / 鉄酸化物 / 移行遅延
Research Abstract

Our research group has been developing a sorption models that consider heterogeneity of surfaces, leading to modeling of the sorption of radionuclides on mineral surfaces. The only phenomenon that the model cannot deal with is sorption reactions involving redox reactions. Since the kinetics of surface redox reactions depend on sorption structures, the routes of electron transfer, etc., understanding such reaction mechanisms is mandatory for the modeling. The purpose of this research is to reveal the routes and the mechanisms of redox reaction of actinide elements at solid/water interaces.
At first, we have developed a laser spectroscopy system that enabled us to follow the temporal evolution of the U(VI)-Fe(II) redox couple. It was turned out that U(IV) was reduced to U(IV) by Fe(II) on the surface of gibbsite, a hydroxide mineral of aluminum, α-Al(OH)_3. The same laser spectroscopy system was also used to investigate the effects of coexisting ligand molecules on the redox reaction and revealed that some chelating ligands found in nature such as citric acid facilitated the reduction of U(VI) by Fe(II) both in bulk solution and on mineral surfaces. We further looked into the ligand effects from the point of electron transfer routes (innersphere vs outersphere electron transfer) and applied the density functional theory for the determination of adsorption structures as well as elucidation of the reduction of adsorbed species.

Report

(4 results)
  • 2007 Annual Research Report   Final Research Report Summary
  • 2006 Annual Research Report
  • 2005 Annual Research Report
  • Research Products

    (13 results)

All 2008 2006 2005

All Journal Article (9 results) (of which Peer Reviewed: 3 results) Presentation (4 results)

  • [Journal Article] Investigation of poor DFT calculations of actinides : Reduction of UO^<2+>_2 ion2006

    • Author(s)
      Hattori, T., Toraishi, T., Tsuneda, T., Tanaka, S.
    • Journal Title

      Lecture Series on Computer and Computational Science ; Recent Progress in Computational Science and Engineering 74

      Pages: 551-554

    • 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] Investigation of poor DFT calculations of actinides : Reduction of UO_2^<2+> ion2006

    • Author(s)
      Hattori, T., Toraishi, T., Tsuneda, T., Tanaka, S.
    • Journal Title

      Lecture Series on Computer and Computational Science ; Recent Progress in Computational Science and Engineering 74

      Pages: 551-554

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] A Theoretical Study on Molecular Structure of Eu(III)-Salicylate Complex in Aqueous System2005

    • Author(s)
      Toraishi, T., Ngasaki, S., Tanaka, S.
    • Journal Title

      Journal of Molecular Structure : THEOCHEM 757

      Pages: 87-97

    • 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] Analysis of Copper Binding in the Ternary System Cu^<2+>/Humic Acid/Goethite at Neutral to Acidic PH2005

    • Author(s)
      Saito, T, Koopal, L. K., Nagasaki, S., Tanaka, S.
    • Journal Title

      Environmental Science & Technology 39

      Pages: 4886-4893

    • 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 Theoretical Study on Molecular Stcuture of Eu(III)-Salicylate Complex in Aqueous System2005

    • Author(s)
      Toraishi, T., Nagasaki, S., Tanaka, S.
    • Journal Title

      Journal of Molecular Structure : THEOCHEM 757

      Pages: 87-97

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Analysis of Copper Binding in the Ternary System Cu^<2+>/Humic Acid/Goethite at Neutral to Acidic pH2005

    • Author(s)
      Saito, T., Koopal, L. K., Nagasaki, S., Tanaka, S.
    • Journal Title

      Environmental Science & Technology 39

      Pages: 4886-4893

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Electrostatic Interaction Models for Ion Binding to Humic Substances2005

    • Author(s)
      Saito, T., Nagasaki, S., Tanaka, S., Koopal, L.K.
    • Journal Title

      Colloids and Surface A 265

      Pages: 104-104

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Analysis of Copper Binding in the Ternary System Cu^<2+>/Humic Acid/Goethite at Neutral to Acidic pH2005

    • Author(s)
      Saito, T., Koopal, L.K., Nagasaki, S., Tanaka, S.
    • Journal Title

      Environmental Science and Technology 39

      Pages: 4886-4886

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Theoretical Study on Molecular Structure of Eu(III)-Salicylate Complexes in Aqueous System2005

    • Author(s)
      Toraishi, T., Nagasaki, S., Tanaka, S.
    • Journal Title

      Journal of Molecular Structure : THEOCHEM 757

      Pages: 87-87

    • Related Report
      2005 Annual Research Report
  • [Presentation] オルトケイ酸存在下でのギブサイト表面へのウラニルの吸着挙動に関する理論計算2008

    • Author(s)
      服部達哉, 石田圭輔, 斉藤拓巳, 常田貴夫, 田中知
    • Organizer
      日本原子力学会「2008年春の年会」
    • Place of Presentation
      大阪大学
    • Year and Date
      2008-03-26
    • Related Report
      2007 Annual Research Report
  • [Presentation] 鉱物-水界面におけるウラニルの吸着に及ぼすオルトケイ酸の影響2006

    • Author(s)
      本多剛, 斉藤拓巳, 長崎晋也, 田中知
    • Organizer
      日本原子力学会, 2006年秋の大会
    • Place of Presentation
      北海道大学
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Ligand-facilitated reduction of uranium by Fe in aqueous solution2006

    • Author(s)
      Honda, T., Toraishi, T., Nagasaki, S., Tanaka, S.
    • Organizer
      IAP 2006
    • Place of Presentation
      Granada, Spain
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Influence of natural organic ligand to U(VI) reduction by Fe(II) in natural underground water environment.2006

    • Author(s)
      Sato, M., Toraishi, T., Nagasaki, S., Tanaka, S.
    • Organizer
      IAP 2006
    • Place of Presentation
      Granada, Spain
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary

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Published: 2005-04-01   Modified: 2016-04-21  

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