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Electrochemical construction of nanostructured copper oxide photocathodes for high performance water-splitting hydrogen gas generation

Research Project

Project/Area Number 19H02810
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 36020:Energy-related chemistry
Research InstitutionToyohashi University of Technology

Principal Investigator

IZAKI MASANOBU  豊橋技術科学大学, 工学(系)研究科(研究院), 教授 (30416325)

Project Period (FY) 2019-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥17,160,000 (Direct Cost: ¥13,200,000、Indirect Cost: ¥3,960,000)
Fiscal Year 2021: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2020: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2019: ¥8,840,000 (Direct Cost: ¥6,800,000、Indirect Cost: ¥2,040,000)
Keywords銅酸化物 / 光電気化学 / 積層体 / ナノ構造体 / 光電変換 / 光カソード / 電気化学 / ナノ混合体 / 量子効率 / エネルギー変換 / 水素生成 / 熱力学 / 水素生成光カソード / Cu2O / CuO / 光電流密度
Outline of Research at the Start

CO2排出量の大幅削減に資する太陽光活用水分解水素生成用高効率光カソードとして適用可能なCuOとCu2Oから構成される積層体・ナノ混合体・超格子ならびにその電気化学製膜法を実現する。電位制御によりCuOとCu2Oを作り分けることができる新規なCu-錯体水溶液を熱力学に立脚して提案・実証し、光電気化学パルス堆積法により積層体からナノ混合体・超格子まで構築する。これにより、大きな光電流密度を実現すると共に、キャリア輸送特性と光カソード特性の定量的解析からナノ構造化効果を解明し、高効率化の指針を明確にする。さらに、電気化学的に表面保護酸化物層を選定・形成し、光カソード安定性を向上させる。

Outline of Final Research Achievements

The bilayer and nanostructured photocathodes composed of 1.5eV-p-CuO and 2.1eV-p-Cu2O have been fabricated by photoelectrochemical reaction, and the photovoltaic characteristics and the dominant factors have been clarified. Both the Cu2O and CuO layers in the CuO/Cu2O bilayer fabricated by electrodeposition followed by heating act as photovoltaic layers resulting in the expansion of the photovoltaic wavelength range. And, the single layers and bilayers of Cu2O and CuO have been fabricated by photoelectrochemical reactions in a Cu-tartrate complex aqueous solution designed based on thermodynamics. The Cu2O/CuO bilayer revealed external quantum efficiency of 56.8 %, and the value enhanced to around 90% by heating under optimized condition. The semiconductor quality, band alignment, and carrier transportation phenomena of them strongly affected the photovoltaic characteristics, that is quantum efficiency.

Academic Significance and Societal Importance of the Research Achievements

本研究により銅酸化物積層体が広い波長範囲の光に対して光電変換機能を有し、高い外部量子効率が実現できること、低コストで拡張性の高い水溶液電気化学プロセスにより形成できることを明らかにした。バンドギャップの異なる複数のp型半導体を含有することは、光カソードや太陽電池用光電変換層において高効率化のための重要な要件であり、従来とは異なるp型半導体層の直接接合型という新規な概念によりその有効性を実証したことは極めて重要である。本研究成果は高効率太陽電池ならびに高効率光電気化学水分解水素生成用光電極の高性能化に直結する成果であり、CO2フリー社会の実現に向けて社会的インパクトは非常に大きい。

Report

(4 results)
  • 2021 Annual Research Report   Final Research Report ( PDF )
  • 2020 Annual Research Report
  • 2019 Annual Research Report
  • Research Products

    (33 results)

All 2022 2021 2020 2019

All Journal Article (8 results) (of which Peer Reviewed: 8 results,  Open Access: 6 results) Presentation (24 results) (of which Int'l Joint Research: 16 results,  Invited: 3 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Structural and Magnetic Characteristics of Hematite and Magnetite Films Prepared by Electrodeposition and Heating2022

    • Author(s)
      Katsuma Daichi、Khoo Pei Loon、Kobayashi Masakazu、Shinagawa Tsutomu、Izaki Masanobu
    • Journal Title

      Journal of The Electrochemical Society

      Volume: 169 Issue: 4 Pages: 042501-042501

    • DOI

      10.1149/1945-7111/ac6247

    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Photoelctrochemically Fabricated and Heated Cu2O/CuO Bilayers with Enhanced Photovoltaic Characteristics2021

    • Author(s)
      Izaki Masanobu、Abe Suzuka、Nakakita Kota、Khoo Pei Loon
    • Journal Title

      ACS Omega

      Volume: 6 Issue: 41 Pages: 27587-27597

    • DOI

      10.1021/acsomega.1c05163

    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Review-Solution Electrochemical Process for Fabricating Metal Oxides and the Thermodynamic Design2021

    • Author(s)
      Izaki Masanobu、Khoo Pei Loon、Shinagawa Tsutomu
    • Journal Title

      Journal of The Electrochemical Society

      Volume: 168 Issue: 11 Pages: 112510-112510

    • DOI

      10.1149/1945-7111/ac371a

    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] High-Resolution Mapping of Local Photoluminescence Properties in CuO/Cu2O Semiconductor Bi-Layers by Using Synchrotron Radiation2021

    • Author(s)
      Kobayashi Masakazu、Izaki Masanobu、Khoo Pei Loon、Shinagawa Tsutomu、Takeuchi Akihisa、Uesugi Kentaro
    • Journal Title

      Materials

      Volume: 14 Issue: 19 Pages: 5570-5570

    • DOI

      10.3390/ma14195570

    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Thermodynamic Design of the Solution Electrochemical Process for Fabricating Smart Oxide and Compound Layers2020

    • Author(s)
      Izaki Masanobu
    • Journal Title

      Journal of the Japan Institute of Metals and Materials

      Volume: 84 Issue: 6 Pages: 177-189

    • DOI

      10.2320/jinstmet.J2020001

    • NAID

      130007846052

    • ISSN
      0021-4876, 1880-6880, 2433-7501
    • Year and Date
      2020-06-01
    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] The Electronic States of Copper Oxides Photoactive Layers Prepared by Electrodeposition followed by Annealing2020

    • Author(s)
      Khoo P L、Satou K、Izaki M
    • Journal Title

      IOP Conference Series: Materials Science and Engineering

      Volume: 920 Issue: 1 Pages: 012028-012028

    • DOI

      10.1088/1757-899x/920/1/012028

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Defect Structure and Photovoltaic Characteristics of Internally Stacked CuO/Cu2O Photoactive Layer Prepared by Electrodeposition and Heating2019

    • Author(s)
      Izaki Masanobu、Fukazawa Kazuma、Sato Kenta、Khoo Pei Loon、Kobayashi Masakazu、Takeuchi Akihisa、Uesugi Kentaro
    • Journal Title

      ACS Applied Energy Materials

      Volume: 2 Issue: 7 Pages: 4833-4840

    • DOI

      10.1021/acsaem.9b00514

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Light-Irradiated Electrochemical Direct Construction of Cu2O/CuO Bilayers by Switching Cathodic/Anodic Polarization in Copper(II)ーTartrate Complex Aqueous Solution2019

    • Author(s)
      Izaki Masanobu、Koyama Takayuki、Khoo Pei Loon、Shinagawa Tsutomu
    • Journal Title

      ACS Omega

      Volume: 5 Issue: 1 Pages: 683-691

    • DOI

      10.1021/acsomega.9b03308

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Presentation] めっき技術を用いた“ものづくり”―鋼から電力・水素までー2022

    • Author(s)
      伊﨑昌伸
    • Organizer
      電気鍍金研究会総会
    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
    • Invited
  • [Presentation] Photocathode properties of photoelectrochemically constructed CuO/Cu2O bi-layers2021

    • Author(s)
      Ryoga Yokoyama, Pei Loon Khoo, Masanobu Izaki
    • Organizer
      INTERFINISH2020
    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Structure and photocathodic characteristics of electrodeposited and annealed p-CuO films2021

    • Author(s)
      Kota Nakakita, Pei Loon Khoo, Masanobu Izaki,
    • Organizer
      INTERFINISH2020
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Photocathode characteristics of CuO-Cu2O nanostructured photoactive layers prepared by photoelectrochemical-potential switching2021

    • Author(s)
      Shinichi Yamamoto, Pei Loon Khoo, Masanobu Izaki
    • Organizer
      INTERFINISH2020
    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Structure and magnetic properties of iron oxide films prepared by electrodeposition2021

    • Author(s)
      Daichi Katsuma, Pei Loon Khoo, Tsutomu Shinagawa, Masanobu Izaki
    • Organizer
      INTERFINISH2020
    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Electrochemical preparation of iron oxide films and the magnetic properties2021

    • Author(s)
      Daichi Katsuma, Pei Loon Khoo, Tsutomu Shinagawa, Masanobu Izaki
    • Organizer
      MRS-J2021
    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Mapping of local photoluminescence properties in CuO/Cu2O semiconductor bi-layers by using focused synchrotron radiation X-ray beam2021

    • Author(s)
      Masakazu Kobayashi, Masanobu Izaki, Pei Loon Khoo, Tsutomu Shinagawa, Akihisa Takeuschi, Kentaro Uesugi
    • Organizer
      MRS-J2021
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 光電気化学電位スイッチングによるCuO-Cu2Oナノ混合体光活性層の形成と光カソード特性2021

    • Author(s)
      山本槙一、Pei Loon Khoo、伊﨑昌伸
    • Organizer
      第23回関西表面技術フォーラム
    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
  • [Presentation] 高量子効率CuO/Cu2O積層体の光電気化学形成2021

    • Author(s)
      Pei Loon Khoo、阿部紗佳、中北幸太、伊﨑昌伸
    • Organizer
      第23回関西表面技術フォーラム
    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
  • [Presentation] Structure and photocathodic characteristics of electrodeposited and annealed p-CuO films2021

    • Author(s)
      Kota Nakakita, Pei Loon Khoo, Masanobu Izaki
    • Organizer
      INTERFINISH2020
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Mapping of local photoluminescence properties in CuO/Cu2O semiconductor bi-layers by using focused synchrotron radiation X-ray beam2021

    • Author(s)
      Masakazu Kobayashi, Masanobu Izaki, Pei Loon Khoo, Tsutomu Shinagawa, Akihisa Takeuschi, Kentaro Uesugi,
    • Organizer
      MRS-J2021
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 光電気化学的に形成したCuO/Cu2O積層体の光カソード特性2021

    • Author(s)
      横山遼河、Pei Loon Khoo、伊﨑昌伸
    • Organizer
      第68回応用物理学会春季学術講演会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 光電気化学電位スイッチングによるCuO-Cu2Oナノ混合体光活性層の形成と光カソード特性2021

    • Author(s)
      山本槙一、Pei Loon Khoo、伊﨑昌伸
    • Organizer
      第68回応用物理学会春季学術講演会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 電気化学的に形成した鉄酸化物膜の構造と磁気的性質2021

    • Author(s)
      勝間大知、Khoo Pei Loon、品川勉、伊﨑昌伸
    • Organizer
      電気化学会第88回大会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 電気化学的に形成したCuO層の光カソード特性2021

    • Author(s)
      中北幸太、Khoo Pei Loon、伊﨑昌伸
    • Organizer
      電気化学会第88回大会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Electrochemical preparation of oxide semiconductors and the application to energy conversion2020

    • Author(s)
      Masanobu Izaki
    • Organizer
      MiNT-SRC International Seminar
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] CuO/Cu2O積層型光活性層の光電気化学的形成2020

    • Author(s)
      阿部紗佳、笹野順司、横山誠二、伊﨑昌伸
    • Organizer
      電気化学会第87会大会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Photoelectrochemical properties and energy state of electrochemically constructed CuO/Cu2O bilayered photocathode2020

    • Author(s)
      R. Yokoyama, P. L. Khoo, and M. Izaki
    • Organizer
      30th Meeting of MRS-J
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Photoelectrochemical characteristics of multi-structured CuO-Cu2O photocathode prepared by electrochemical potential switching2020

    • Author(s)
      S. Yamamoto, P. L. Khoo, and M. Izaki
    • Organizer
      30th Meeting of MRS-J
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Improved photoactivity for electrochemically prepared and heated fan-shaped CuO photocathode2020

    • Author(s)
      K. Nakakita, P. L. Khoo, and M. Izak
    • Organizer
      30th Meeting of MRS-J
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Photovoltaic oxide layers and the devices prepared by solution chemical processing2020

    • Author(s)
      M. Izaki
    • Organizer
      30th Meeting of MRS-J
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Potentially controlled electrochemical deposition of single and stacked copper(I) oxide and copper(II) oxide photoactive layers2019

    • Author(s)
      Pei Loon Khoo, Takayuki Koyama, Masanobu izaki
    • Organizer
      第16回次世代の太陽光発電システムシンポジウム
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Electrochemically prepared copper(I) oxide/copper(II) oxide photoactive multilayers from a single solution by potential control,2019

    • Author(s)
      Pei Loon Khoo, Takayuki Koyama, Masanobu izaki,
    • Organizer
      E-MRS 2019 Fall Meeting
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] EQE, XPS and the electronic states of copper oxides photoactive layers prepared by electrodeposition-annealing2019

    • Author(s)
      Pei Loon Khoo, Kenta Sato, Masanobu izaki,
    • Organizer
      6th International Conference of Global Network for Innovative Technology
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Patent(Industrial Property Rights)] 光活性層及びその製造方法2019

    • Inventor(s)
      伊﨑昌伸、他4名
    • Industrial Property Rights Holder
      伊﨑昌伸、他4名
    • Industrial Property Rights Type
      特許
    • Filing Date
      2019
    • Related Report
      2019 Annual Research Report

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Published: 2019-04-18   Modified: 2023-01-30  

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