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2019 Fiscal Year Annual Research Report

Sensitizers Immobilized on Semiconducting Electrodes for Light Energy Conversion

Research Project

Project/Area Number 18H03898
Research InstitutionKyoto University

Principal Investigator

今堀 博  京都大学, 工学研究科, 教授 (90243261)

Project Period (FY) 2018-04-01 – 2021-03-31
Keywords人工光合成 / 有機太陽電池 / ポルフィリン / 水酸化触媒 / 半導体電極 / 銅錯体
Outline of Annual Research Achievements

人工光合成は可視光を利用した物質変換を目指す研究であるが、現状では非常に低い性能にとどまっている。天然の光合成では、光捕集系で獲得されたエネル ギーを用いて、反応中心タンパク質で一連の電子移動反応を行い、一方水酸化触媒から電子を奪うことで高活性な酸化種を生み出し、水からの電子引き抜き、酸 素発生を可能にしている。本提案では上記の過程を人工的に模倣し、可視光物質変換機構を詳細に解明することで、人工光合成の高効率化を目指している。具体的には、可視光を捕集可能な酸化力の強い光増感分子を合成し、水酸化触媒分子と共に半導体電極上に固定化し、可視光応答型水分解セルを構築した。特に水酸化触媒分子において、触媒活性部位と半導体電極への固定化部位の間の距離を変化させることを試み、予備的ながらもその距離依存性を見出した。一方、上記の 分子を用いた人工光合成は色素増感太陽電池と共通する点が多く、色素増感太陽電池の高効率化から得られる情報は人工光合成においても有用と思われる。いずれの系においても、太陽光の効率的な利用は高性能化に必須である。そこで色素増感太陽電池において、可視光・近赤外光の効率的な捕集が原理的に可能なポルフィリンに着目した。具体的には、置換メチレン構造で縮環したプッシュ・プル型のポルフィリン色素を分子設計・合成し、現在知られている最も性能の高いポルフィリン色素GY50を上回る太陽電池性能を達成することができた。また、高い開放電圧が期待できる一連の新規な銅レドックス対を分子設計・合成し、光電変換特性との相関を解明することができた。

Current Status of Research Progress
Current Status of Research Progress

2: Research has progressed on the whole more than it was originally planned.

Reason

色素増感太陽電池においては、新規な分子設計で光増感色素を合成し、現在知られている最も性能の高い色素の一つであるGY50を上回る太陽電池性能を達成でき たことは大きな進展である。また、高効率化に向けて必須な新規な銅レドックス対を分子設計・合成し、光電変換特性との相関を解明することができている。一方、人工光合成に関しては、可視光水分解の機構解明に取り組むための評価系構築を進めている段階である。

Strategy for Future Research Activity

色素増感太陽電池においては、今回得られた基礎的知見をフィードバックさせ、さらなる太陽電池性能向上を目指す。一方、人工光合成に関しては、触媒活性部位と半導体電極への固定化部位の間の距離を系統的に変化させ、可視光水分解活性との相関解明を試みる。また、p-型半導体に光増感色素を担持した系の開発を進める。

Remarks

有機太陽電池に関する研究成果はプレスリリースされ、新聞、雑誌などの国内外のメディアで取り上げられた。

  • Research Products

    (29 results)

All 2020 2019 Other

All Int'l Joint Research (3 results) Journal Article (14 results) (of which Int'l Joint Research: 3 results,  Peer Reviewed: 14 results,  Open Access: 2 results) Presentation (9 results) (of which Int'l Joint Research: 8 results,  Invited: 9 results) Remarks (3 results)

  • [Int'l Joint Research] Tampere University of Technology(フィンランド)

    • Country Name
      FINLAND
    • Counterpart Institution
      Tampere University of Technology
  • [Int'l Joint Research] Tongji University(中国)

    • Country Name
      CHINA
    • Counterpart Institution
      Tongji University
  • [Int'l Joint Research] Karlsruhe Institute of Technology(ドイツ)

    • Country Name
      GERMANY
    • Counterpart Institution
      Karlsruhe Institute of Technology
  • [Journal Article] Effect of Ligand Structures of Copper Redox Shuttles on Photovoltaic Performance of Dye-Sensitized Solar Cells2020

    • Author(s)
      T. Higashino, H. IIyama, S. Nimura, Y. Kurumisawa, and H. Imahori
    • Journal Title

      Inorg. Chem.

      Volume: 59 Pages: 452-459

    • DOI

      10.1021/acs.inorgchem.9b02740

    • Peer Reviewed
  • [Journal Article] Modulation of Frontier Molecular Orbitals on Dithieno[3,4-b:3’,4’-d]phosphole Derivatives by Donor-pi-Acceptor Interaction2020

    • Author(s)
      T. Higashino, K. Ishida, and H. Imahori
    • Journal Title

      Chem. Lett.

      Volume: 49 Pages: 272-275

    • DOI

      10.1246/cl.190879

    • Peer Reviewed
  • [Journal Article] Sustained Photodynamic Effect of Single Chirality-Enriched Single-Walled Carbon Nanotubes2020

    • Author(s)
      R. Fukuda, T. Umeyama, M. Tsujimoto, F. Ishidate, T. Tanaka, H. Kataura, H. Imahori, and T. Murakami
    • Journal Title

      Carbon

      Volume: 161 Pages: 718-725

    • DOI

      10.1016/j.carbon.2020.02.002

    • Peer Reviewed
  • [Journal Article] Effects of meso-Diarylamino Group of Porphyrins on Optical and Electrochemical Properties2020

    • Author(s)
      T. Higashino, Y. Fujimori, I. Nishimura, and H. Imahori
    • Journal Title

      J. Porphyrins Phthalocyanines

      Volume: 24 Pages: 67-74

    • DOI

      10.1142/S1088424619500652

    • Peer Reviewed
  • [Journal Article] Efficient Light-Harvesting, Energy Migration, and Charge Transfer by Nanographene-Based Nonfullerene Acceptor Small-Molecule Exhibiting Unusually Long Excited-State Lifetime in Film State2020

    • Author(s)
      T. Umeyama, K. Igarashi, D. Sasada, Y. Tamai, K. Ishida, T. Koganezawa, S. Ohtani, K. Tanaka, H. Ohkita, and H. Imahori
    • Journal Title

      Chem. Sci.

      Volume: 11 Pages: 3250-3257

    • DOI

      10.1039/C9SC06456G

    • Peer Reviewed / Open Access
  • [Journal Article] Pluripotent Features of Doubly Thiophene-Fused Benzodiphospholes as Organic Functional Materials2019

    • Author(s)
      T. Higashino, K. Ishida, T. Sakurai, S. Seki, T. Konishi, K. Kamada, K. Kamada, and H. Imahori
    • Journal Title

      Chem. Eur. J.

      Volume: 25 Pages: 6425-6438

    • DOI

      10.1002/chem.201900661

    • Peer Reviewed
  • [Journal Article] Renaissance of Fused Porphyrins: Substituted Methylene-bridged Thiophene-Fused Strategy for High-Performance Dye-Sensitized Solar Cells2019

    • Author(s)
      Y. Kurumisawa, T. Higashino, S. Nimura, Y. Tsuji, H. Iiyama, and H. Imahori
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 141 Pages: 9910-9919

    • DOI

      10.1021/jacs.9b03302

    • Peer Reviewed
  • [Journal Article] Exclusive Occurrence of Photoinduced Energy Transfer and Switching Its Direction by Rectangular π-Extension of Nanographenes2019

    • Author(s)
      T. Umeyama, T. Hanaoka, H. Yamada, Y. Namura, S. Mizuno, T. Ohara, J. Baek, J. Park, Y. Takano, K. Stranius, N. V. Tkachenko, and H. Imahori
    • Journal Title

      Chem. Sci.

      Volume: 10 Pages: 6642-6650

    • DOI

      10.1039/c9sc01538h

    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Photoconductivity in Metal-Organic Framework (MOF) Thin Films2019

    • Author(s)
      X. Liu, M. Kozlowska, T. Okkali, D. Wagner, T. Higashino, G. Brenner-Weis, S. Marschner, Z. Fu, Q. Zhang, H. Imahori, S. Brase, W. Wenzel, C. Woll, and L. Heinke
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 58 Pages: 9590-9595

    • DOI

      10.1002/anie.201904475

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Thiazolocatechol: Electron-withdrawing Catechol Anchoring Group for Dye-Sensitized Solar Cells2019

    • Author(s)
      T. Higashino, H. Iiyama, Y. Kurumisawa, and H. Imahori
    • Journal Title

      ChemPhysChem

      Volume: 20 Pages: 2689-2695

    • DOI

      10.1002/cphc.201900342

    • Peer Reviewed
  • [Journal Article] Isomer Effects of Fullerene Derivatives on Organic Photovoltaics and Perovskite Solar Cells2019

    • Author(s)
      T. Umeyama and H. Imahori
    • Journal Title

      Acc. Chem. Res.

      Volume: 52 Pages: 2046-2055

    • DOI

      10.1021/acs.accounts.9b00159

    • Peer Reviewed
  • [Journal Article] Effective Role of Eco-Friendly Acetyl Tributyl Citrate in Large-Scale Catalyst-Free Synthesis of Waterborne Polyurethanes Without Volatile Organic Compounds2019

    • Author(s)
      X.-G. Li, Y.-B. Xie, M.-R. Huang, T. Umeyama, T. Ohara and H. Imahori
    • Journal Title

      J. Clean. Prod.

      Volume: 237 Pages: 117543-1-16

    • DOI

      10.1016/j.jclepro.2019.07.018

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Spontaneous Complexation of Fullerenes on Nanodiamond Aggregates and Their Enhanced Photocurrent Generation2019

    • Author(s)
      T. Umeyama, Y. Okawada, T. Ohara, and H. Imahori
    • Journal Title

      Chem. Asian J.

      Volume: 14 Pages: 4042-4047

    • DOI

      10.1002/asia.201900835

    • Peer Reviewed
  • [Journal Article] Phosphole-Fused Dehydropurpurins via Titanium-Mediated [2+2+1] Cyclization Strategy2019

    • Author(s)
      T. Higashino, I. Nishimura, and H. Imahori
    • Journal Title

      Chem. Eur. J.

      Volume: 25 Pages: 13816-13823

    • DOI

      10.1002/chem.201903269

    • Peer Reviewed
  • [Presentation] Donor-Acceptor Interactions for Energy and Biological Applications2020

    • Author(s)
      H. Imahori
    • Organizer
      86th Annual Meeting of the Chemical Society of Japan
    • Invited
  • [Presentation] Model Systems and Organic Solar Cells for Solar Energy Conversion2019

    • Author(s)
      H. Imahori
    • Organizer
      Pre-ECS Symposium
    • Int'l Joint Research / Invited
  • [Presentation] Isomer Effects of Nanocarbons in Organic Solar Cells2019

    • Author(s)
      H. Imahori
    • Organizer
      235th Meeting of The Electrochemical Society
    • Int'l Joint Research / Invited
  • [Presentation] Porphyrins as Excellent Sensitizers and Electron and Energy Donors2019

    • Author(s)
      H. Imahori
    • Organizer
      The First Asian Conference on Porphyrins, Phthalocyanines, and Related Materials (ACPP-1)
    • Int'l Joint Research / Invited
  • [Presentation] Model Systems and Organic Solar Cells toward Highly Efficient Solar Energy Conversion2019

    • Author(s)
      H. Imahori
    • Organizer
      The 9th East Asia Symposium on Functional Dyes and Advanced Materials
    • Int'l Joint Research / Invited
  • [Presentation] Donor-Acceptor Interaction for Solar Energy Conversion2019

    • Author(s)
      H. Imahori
    • Organizer
      The 1st Kyoto University -UNIST Joint Symposium on Chemistry and Materials Science
    • Int'l Joint Research / Invited
  • [Presentation] Donor-Acceptor Interactions for Solar Energy Conversion2019

    • Author(s)
      H. Imahori
    • Organizer
      2019 National Chung Hsing University-Kyoto University Symposium on Advanced Chemistry
    • Int'l Joint Research / Invited
  • [Presentation] Model Systems and Organic Photovoltaics2019

    • Author(s)
      H. Imahori
    • Organizer
      The 10th Asian Conference on Electrochemical Power Sources 2019
    • Int'l Joint Research / Invited
  • [Presentation] Model Systems for Photosynthesis and Organic Photovoltaics2019

    • Author(s)
      H. Imahori
    • Organizer
      The 18th Asian Chemcial Congress (ACC) and 20th General Assembly of the Federation of Asian Chemcial Societies (FACS)
    • Int'l Joint Research / Invited
  • [Remarks] 最近の論文から

    • URL

      http://www.moleng.kyoto-u.ac.jp/~moleng_05/research_paper.html

  • [Remarks] 新規色素設計指針を開発 -世界最高の太陽光エネルギー変換効率の実現に向けて-

    • URL

      http://www.kyoto-u.ac.jp/ja/research/research_results/2019/190613_2.html

  • [Remarks] 新しい電子受容性材料の設計指針を開発 -有機薄膜太陽電池をより高効率により簡便に-

    • URL

      http://www.kyoto-u.ac.jp/ja/research/research_results/2019/200306_1.html

URL: 

Published: 2021-01-27  

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