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Clarification of Mechanisms for Surface Photoreactions and Improvement of Photocatalytic Activity for Visible-light Responsive Metal Oxides

Research Project

Project/Area Number 16350114
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic industrial materials
Research InstitutionOsaka University

Principal Investigator

NAKATO Yoshihiro  Osaka University, Graduate School of Engineering Science, Professor, 大学院・基礎工学研究科, 教授 (70029502)

Co-Investigator(Kenkyū-buntansha) IMANISHI Akihito  Osaka University, Graduate School of Engineering Science, Associate Professor, 大学院・基礎工学研究科, 助教授 (60304036)
Project Period (FY) 2004 – 2005
Project Status Completed (Fiscal Year 2005)
Budget Amount *help
¥16,100,000 (Direct Cost: ¥16,100,000)
Fiscal Year 2005: ¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 2004: ¥13,100,000 (Direct Cost: ¥13,100,000)
Keywordssolar energy / photocatalyst / metal oxides / nanoparticles / photoluminescene / reaction mechanism / oxygen evolution / surface structural control / 表面分光法
Research Abstract

With an aim to improve the activity of TiO_2 and related metal-oxide photocatalysts for solar water splitting and photodecomposition of harmful organic compounds, we have studied molecular mechanisms of surface photoreactions on TiuO_2 (rutile) and explored new active visible-light responsive metal-oxide photocatalysts. At first, we have succeeded in preparing atomically flat and stable n-TiO_2 (rutile) (110) and (100) surfaces by a novel method of HF-etching and annealing at 550℃. This success has for the first time enabled us to reveal interesting crystal-face dependences of important properties of TiO_2 (rutile), such as the flat-band potential (U_<fb>), the hole reactivity, and the photoluminescense (PL) spectrum which arises from a precursor (called surface-trapped hole, s.t.h.) of photooxidation reaction of water on TiO_2. In addition, we have clarified that the occurrence of the photooxidation reaction of water on the atomically flat TiO_2 (110) and (100) surfaces has led to their roughening on an atomic scale together with weakening of the PL intensity. These results have been explained well by our recently proposed mechanism that the photooxidation reaction of water on TiO_2 is initiated by a nucleophilic attack of water (Lewis base) to the surface-trapped hole (s.t.h.) (Lewis acid), giving strong support to the mechanism. In order to investigate further the validity of the mechanism, we have also studied the mechanism for the water photooxidation reaction on nitrogen-containing metal oxides, such as N-doped TiO_2 and TaON, and found that the reaction proceeds by the same mechanism as on TiO_2 as well. Furthermore, we have explored new visible-light responsive metal-oxide photocatalysts and found that mixed metal oxides such as BiCu_2VO_6 and BiZn_2VO_6 show higher activity that BiVO_4 that is known as one of the most active visible-light driven photocatalysts.

Report

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

    (27 results)

All 2006 2005 2004 Other

All Journal Article (24 results) Patent(Industrial Property Rights) (3 results)

  • [Journal Article] A Novel Visible-Light Responsive Photocatalyst, BiZn_2VO_6, for Efficient Oxygen Photoevolution from Aqueous Particulate Suspensions2006

    • Author(s)
      H.M.Liu, et al.
    • Journal Title

      Electrochem.Solid-State Lett. 9・5

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] A Visible-Light Responsive Photocatalyst, BiZn_2VO_6, for Efficient Oxygen Photoevolution from Aqueous Particulate Suspensions2006

    • Author(s)
      H.M.Liu, R.Nakamura, Y.Nakato
    • Journal Title

      Electrochem.Solid-State Lett. 9(5)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Crystal-Face Dependences of Surface Band Edges and Hole Reactivity, Revealed by Preparation of Atomically-smooth and Stable (110) and (100) n-TiO_2 (Rutile) Surfaces,2005

    • Author(s)
      Ryuhei Nakamura, et al.
    • Journal Title

      J.Phys.Chem.B 109・5

      Pages: 1648-1651

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Oxygen Photoevolution on a Tantalum Oxynitride Photocatalyst under Visible-light Irradiation : How Does Water Photooxidation Proceed on a Metal Oxynitride Surface?2005

    • Author(s)
      R.Nakamura, et al.
    • Journal Title

      J.Phys.Chem.B 109

      Pages: 8920-8927

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Annual Research Report 2005 Final Research Report Summary
  • [Journal Article] Promoted Photooxidation Reactivity of Particulate BiVO_4 Photocatalyst Prepared by a Photoassisted Sol-gel Method2005

    • Author(s)
      H.M.Liu, et al.
    • Journal Title

      J.Electrochem.Soc. 152(11)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Molecular Mechanisms of Photo-induced Oxygen Evolution, PL Emission, and Surface Roughening at Atomically Smooth (110) and (100) n-TiO_2 (Rutile) Surfaces in Aqueous Acidic Solutions2005

    • Author(s)
      R.Nakamura, et al.
    • Journal Title

      J.Am.Chem.Soc. 127

      Pages: 12975-12983

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Annual Research Report 2005 Final Research Report Summary
  • [Journal Article] Bismuth Copper Vanadate BiCu_2VO_6 as a Novel Photocatalyst for Efficient Visible-Light-Driven Oxygen Evolution,2005

    • Author(s)
      H.M.Liu, et al.
    • Journal Title

      Chem.Phys.Chem. 6

      Pages: 2499-2502

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Crystal-Face Dependences of Surface Band Edges and Hole Reactivity, Revealed by Preparation of Essentially Atomically-smooth and Stable(110) and (100) n-TiO_2 (Rutile) Surfaces2005

    • Author(s)
      R.Nakamura, N.Ohashi, A.Imanishi, T.Osawa, Y.Matsumoto, H.Koinuma, Y.Nakato
    • Journal Title

      J.Phys.Chem.B 109

      Pages: 1648-1651

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Oxynitride Photocatalyst on a Tantalum Oxynitride Photocatalyst under Visible-light Irradiation : How Does Water Photooxidation Proceed on a Metal-Oxynitride Surface?2005

    • Author(s)
      R.Nakamura, T.Tanaka, Y.Nakato
    • Journal Title

      J.Phys.Chem.B 109

      Pages: 8920-8927

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Promoted Photooxidation Reactivity of Particulate BiVO_4 Photocatalyst Prepared by a Photoassisted Sol-gel Method2005

    • Author(s)
      R.Nakamura, T.Tanaka, Y.Nakato, H.M.Liu, R.Nakamura, Y.Nakato
    • Journal Title

      J.Electrochem.Soc. 152(11)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Molecular Mechanisms of Photo-induced Oxygen Evolution, PL Emission, and Surface Roughening at Atomically Smooth(110) and (100) n-TiO_2(Rutile) Surfaces in Aqueous Acidic Solutions2005

    • Author(s)
      R.Nakamura, T.Okamura, N.Ohashi, A.Imanishi, Y.Nakato
    • Journal Title

      J.Am.Chem.Soc. 127

      Pages: 12975-12983

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Bismuth Copper Vanadate BiCu_2VO_6 as a Novel Photocatalyst for Efficient Visible-Light-Driven Oxygen Evolution2005

    • Author(s)
      H.M.Liu, R.Nakamura, Y.Nakato
    • Journal Title

      Chem.Phys.Chem. 6

      Pages: 2499-2502

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Crystal-Face Dependences of Surface Band Edges and Hole Reactivity, Revealed by Preparation of Essentially Atomically-smooth and Stable (110) and (100) n-TiO_2 (Rutile) Surfaces2005

    • Author(s)
      R.Nakamura, et al.
    • Journal Title

      J.Phys.Chem.B 109

      Pages: 1648-1651

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Promoted Photoxidation Reactivity of Particulate BiVO_4 Photocatalyst Prepared by a Photoassisted Sol-gel Method2005

    • Author(s)
      H.M.Liu, et al.
    • Journal Title

      J.Electrochem.Soc. 152(11)

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Bismuth Copper Vanadate BiCu_2Vo_6 as a Novel Photocatalyst for Efficient Visible-Light-Driven Oxygen Evolution,2005

    • Author(s)
      H.M.Liu, et al.
    • Journal Title

      Chem.Phys.Chem. 6

      Pages: 2499-2502

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Crystal-Face Dependences of Surface Band Edges and Hole Reactivity, Revealed by Preparation of Atomically-smooth and Stable(110) and (100) n-TiO_2 (Rutile) Surfaces.2005

    • Author(s)
      Ryuhei Nakamura, et al.
    • Journal Title

      J.Phys.Chem.B 109・5

      Pages: 1648-1651

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Primary Intermediates of Oxygen Photoevolution Reaction on TiO_2 (Rutile) Particles, Revealed by in Situ FTIR Absorption and Photoluminescence Measurements2004

    • Author(s)
      Ryuhei Nakamura, et al.
    • Journal Title

      J.Am.Chem.Soc. 126

      Pages: 1290-1298

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] A Nano-Modified Si/TiO_2 Composite Electrode for Efficient Solar Water Splitting2004

    • Author(s)
      S.Takabayashi, et al.
    • Journal Title

      J.Photochem.Photobiol.A : Chemistry 166・1-3

      Pages: 107-113

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Mechanism for Visible Light Responses in Anodic Photocurrents at N-doped TiO_2 Film Electrodes2004

    • Author(s)
      Ryuhei Nakamura, et al.
    • Journal Title

      J.Phys.Chem.B 108・30

      Pages: 10617-10620

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary 2004 Annual Research Report
  • [Journal Article] Primary Intermediates of Oxygen Photoevolution Reaction on TiO_2(Rutile) Particles, Revealed by In Situ FTIR Absorption and Photoluminescene Measurements2004

    • Author(s)
      R.Nakamura, Y.Nakato
    • Journal Title

      J.Am.Chem.Soc. 126

      Pages: 1290-1298

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] A Nano-Modified Si/TiO_2 Composite Electrode for Efficient Solar Water Splitting2004

    • Author(s)
      S.Takabayashi, R.Nakamura, Y.Nakato
    • Journal Title

      J.Photochem.Photobiol.A : Chemistry 166(1-3)

      Pages: 107-113

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Mechanism for Visible Light Responses in Anodic Photocurrents at N-doped TiO_2 Film Electrodes2004

    • Author(s)
      R.Nakamura, T.Tanaka, Y.Nakato
    • Journal Title

      J.Phys.Chem.B 108

      Pages: 10617-10620

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] A Novel Visible-Light Responsive Photocatalyst, BiZn_2VO_6,for Efficient Oxygen Photoevolution from Aqueous Particulate Suspensions

    • Author(s)
      H.M.Liu, et al.
    • Journal Title

      Electrochem.Solid-State Lett. (in press)

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Oxygen Photoevolution on a Tantalum Oxynitride Photocatalyst under Visible-Light Irradiation : How Does Water Photooxidation Proceed on a Metal Oxynitride Surface?

    • Author(s)
      Ryuhei Nakamura, et al.
    • Journal Title

      J.Phys.Chem.B (In press)

    • Related Report
      2004 Annual Research Report
  • [Patent(Industrial Property Rights)] 高い反応効率を有する光触媒2005

    • Inventor(s)
      中戸義禮他
    • Industrial Property Rights Holder
      中戸義禮他
    • Filing Date
      2005-03-01
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Patent(Industrial Property Rights)] 可視光応答性を有する複合金属酸化物光触媒2005

    • Inventor(s)
      中戸義禮他
    • Industrial Property Rights Holder
      中戸義禮他
    • Filing Date
      2005-12-15
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Patent(Industrial Property Rights)] 可視光応答性を有する複合金属酸化物光触媒2004

    • Inventor(s)
      中戸義禮他
    • Industrial Property Rights Holder
      中戸義禮他
    • Industrial Property Number
      2004-359355
    • Filing Date
      2004-12-13
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary

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Published: 2004-04-01   Modified: 2016-04-21  

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