Sensitizers Immobilized on Semiconducting Electrodes for Light Energy Conversion

• Project/Area Number: 18H03898
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Medium-sized Section 32:Physical chemistry, functional solid state chemistry, and related fields
• Research Institution: Kyoto University
• Principal Investigator: IMAHORI Hiroshi 京都大学, 工学研究科, 教授 (90243261)
• Project Period (FY): 2018-04-01 – 2021-03-31
• Project Status: Completed (Fiscal Year 2020)
• Budget Amount: ¥44,070,000 (Direct Cost: ¥33,900,000、Indirect Cost: ¥10,170,000); Fiscal Year 2020: ¥14,430,000 (Direct Cost: ¥11,100,000、Indirect Cost: ¥3,330,000); Fiscal Year 2019: ¥14,430,000 (Direct Cost: ¥11,100,000、Indirect Cost: ¥3,330,000); Fiscal Year 2018: ¥15,210,000 (Direct Cost: ¥11,700,000、Indirect Cost: ¥3,510,000)
• Keywords: 人工光合成 / 色素増感太陽電池 / ポルフィリン / 有機太陽電池 / 水酸化触媒 / 半導体電極 / 銅錯体 / 太陽エネルギー変換 / 増感剤 / 増感色素

Outline of Final Research Achievements

Artificial photosynthesis is a research field focusing on material conversion by visible light, but the performance is still poor. In this project we aimed to mimic photosynthetic processes artificially and elucidate the underlying mechanism toward efficient energy conversion. We developed photoelectrochemical cells with a semiconducting electrode modified with water oxidation catalysts and molecular sensitizers with visible light-harvesting and high oxidation ability. A remarkably high power conversion efficiency was also achieved by dye-sensitized solar cells with push-pull type fused porphyrins.

Academic Significance and Societal Importance of the Research Achievements

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、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原理を明らかにできた。以上の研究成果は、今後の高効率太陽エネルギー変換に向けて重要な基礎的知見となりうる。

Research Products

• [Int'l Joint Research] The Arctic University of Norway(ノルウェー)
• [Int'l Joint Research] Tampere University of Technology(フィンランド)
• [Int'l Joint Research] Tongji University(中国)
• [Int'l Joint Research] Karlsruhe Institute of Technology(ドイツ)
• [Int'l Joint Research] Tampere University of Technology(フィンランド)
• [Int'l Joint Research] Tongji University(中国)
• [Journal Article] Exploration on the Combination of Push-Pull Porphyrin Dyes and Copper(I/II) Redox Shuttles toward High-Performance Dye-Sensitized Solar Cells (2020)
  • Author(s): T. Higashino, H. Iiyama, I. Nishimura, and H. Imahori
  • Journal Title: Chem. Lett. Volume: 49 Issue: 8 Pages: 936-939
  • DOI: 10.1246/cl.200317
  • NAID: 130007884738
  • Peer Reviewed
• [Journal Article] Unique Role of Heterole-fused Structures in Aromaticity and Physicochemical Properties of 7,8-Dehydropurpurins (2020)
  • Author(s): T. Higashino, I. Nishimura, and H. Imahori
  • Journal Title: Chem. Eur. J. Volume: 52 Issue: 52 Pages: 12043-12049
  • DOI: 10.1002/chem.202001361
  • Peer Reviewed
• [Journal Article] Heavy Metal Effects on the Photovoltaic Properties of Metallocorroles in Dye-Sensitized Solar Cells (2020)
  • Author(s): Tomohiro Higashino, Yuma Kurumisawa, Abraham B. Alemayehu, Rune F. Einrem, Debashis Sahu, Daniel Packwood, Kosaku Kato, Akira Yamakata, Abhik Ghosh and Hiroshi Imahori
  • Journal Title: ACS Applied Energy Materials Volume: 3 Issue: 12 Pages: 12460-12467
  • DOI: 10.1021/acsaem.0c02427
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Effect of Ligand Structures of Copper Redox Shuttles on Photovoltaic Performance of Dye-Sensitized Solar Cells (2020)
  • Author(s): T. Higashino, H. IIyama, S. Nimura, Y. Kurumisawa, and H. Imahori
  • Journal Title: Inorg. Chem. Volume: 59 Issue: 1 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 Interaction (2020)
  • Author(s): T. Higashino, K. Ishida, and H. Imahori
  • Journal Title: Chem. Lett. Volume: 49 Issue: 3 Pages: 272-275
  • DOI: 10.1246/cl.190879
  • NAID: 130007805929
  • Peer Reviewed
• [Journal Article] Sustained photodynamic effect of single chirality-enriched single-walled carbon nanotubes (2020)
  • Author(s): Fukuda, R.; Umeyama, T.; Tsujimoto, M.; Ishidate, F.; Tanaka, T.; Kataura, H.; Imahori, H.; Murakami, T.
  • Journal Title: Carbon Volume: 161 Pages: 718-725
  • DOI: 10.1016/j.carbon.2020.02.002
  • Peer Reviewed / Open Access
• [Journal Article] Effects of meso-Diarylamino Group of Porphyrins on Optical and Electrochemical Properties (2020)
  • Author(s): T. Higashino, Y. Fujimori, I. Nishimura, and H. Imahori
  • Journal Title: J. Porphyrins Phthalocyanines Volume: 24 Issue: 01n03 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 State (2020)
  • 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 Issue: 12 Pages: 3250-3257
  • DOI: 10.1039/c9sc06456g
  • Peer Reviewed / Open Access
• [Journal Article] Pluripotent Features of Doubly Thiophene‐Fused Benzodiphospholes as Organic Functional Materials (2019)
  • Author(s): Higashino Tomohiro、Ishida Keiichi、Sakurai Tsuneaki、Seki Shu、Konishi Tatsuki、Kamada Kenji、Kamada Kenji、Imahori Hiroshi
  • Journal Title: Chemistry - A European Journal Volume: 印刷中 Issue: 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 Cells (2019)
  • Author(s): Y. Kurumisawa, T. Higashino, S. Nimura, Y. Tsuji, H. Iiyama, and H. Imahori
  • Journal Title: J. Am. Chem. Soc. Volume: 141 Issue: 25 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 Nanographenes (2019)
  • 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 Issue: 27 Pages: 6642-6650
  • DOI: 10.1039/c9sc01538h
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Photoconductivity in Metal-Organic Framework (MOF) Thin Films (2019)
  • 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 Issue: 28 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 Cells (2019)
  • Author(s): T. Higashino, H. Iiyama, Y. Kurumisawa, and H. Imahori
  • Journal Title: ChemPhysChem Volume: 20 Issue: 20 Pages: 2689-2695
  • DOI: 10.1002/cphc.201900342
  • Peer Reviewed
• [Journal Article] Isomer Effects of Fullerene Derivatives on Organic Photovoltaics and Perovskite Solar Cells (2019)
  • Author(s): T. Umeyama and H. Imahori
  • Journal Title: Acc. Chem. Res. Volume: 52 Issue: 8 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 Compounds (2019)
  • 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: 117543-117543
  • 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 Generation (2019)
  • Author(s): T. Umeyama, Y. Okawada, T. Ohara, and H. Imahori
  • Journal Title: Chem. Asian J. Volume: 14 Issue: 22 Pages: 4042-4047
  • DOI: 10.1002/asia.201900835
  • Peer Reviewed
• [Journal Article] Phosphole-Fused Dehydropurpurins via Titanium-Mediated [2+2+1] Cyclization Strategy (2019)
  • Author(s): T. Higashino, I. Nishimura, and H. Imahori
  • Journal Title: Chem. Eur. J. Volume: 25 Issue: 60 Pages: 13816-13823
  • DOI: 10.1002/chem.201903269
  • Peer Reviewed
• [Journal Article] Cleaner Synthesis and Systematical Chracterization of Sustainable Poly(isosorbide-co-ethylene terephthalate) by Environ-Benign and Highly Active Catalysts (2019)
  • Author(s): X.-G. Ki, G. Song, M.-R. Huang, T. Ohara, H. Yamada, T. Umeyama, T. Higashino, and H. Imahori
  • Journal Title: J. Clean. Prod. Volume: 206 Pages: 483-497
  • DOI: 10.1016/j.jclepro.2018.09.046
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Synthesis of Phosphole-bridged Porphyrin Dimers (2019)
  • Author(s): Higashino Tomohiro、Nishimura Issei、Imahori Hiroshi
  • Journal Title: Chemistry Letters Volume: 48 Issue: 3 Pages: 257-259
  • DOI: 10.1246/cl.180943
  • NAID: 130007607563
  • Peer Reviewed
• [Journal Article] cis-1 Isomers of Tethered Bismethano[70]fullerene as Electron Acceptors in Organic Photovoltaics (2018)
  • Author(s): T. Umeyama, S. Takahara, S. Shibata, K. Igarashi, T. Higashino, K. Mishima, K. Yamashita, and H. Imahori
  • Journal Title: RSC Adv. Volume: 8 Issue: 33 Pages: 18316-18326
  • DOI: 10.1039/c8ra02896f
  • NAID: 120006534623
  • Peer Reviewed / Open Access
• [Journal Article] Enhanced Donor-π-Acceptor Character of A Porphyrin Dye Incorporating Naphthobisthiadiazole for Efficient Near Infrared Light Absorption (2018)
  • Author(s): T. Higashino, Y. Kurumisawa, S. Nimura, H. Iiyama, and H. Imahori
  • Journal Title: Eur. J. Org. Chem. Volume: 2018 Issue: 20-21 Pages: 2537-2547
  • DOI: 10.1002/ejoc.201701736
  • Peer Reviewed
• [Journal Article] Photophysical Properties of Porphyrin Dimer-Single-Walled Carbon Nanotube Linked Systems (2018)
  • Author(s): J. Baek, T. Umeyama, S. Mizuno, N. V. Tkachenko, and H. Imahori
  • Journal Title: J. Phys. Chem. C Volume: 印刷中 Issue: 25 Pages: 13285-13293
  • DOI: 10.1021/acs.jpcc.7b08594
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Unique Tube-Ring Interactions: Complexation of Single-Walled Carbon Nanotubes with Cycloparaphenyleneacetylenes (2018)
  • Author(s): K. Miki, K. Saiki, T. Umeyama, J. Baek, T. Noda, H. Imahori, Y. Sato, K. Suenaga, and K. Ohe
  • Journal Title: Small Volume: 14 Issue: 26
  • DOI: 10.1002/smll.201800720
  • NAID: 120006540187
  • Peer Reviewed
• [Journal Article] Calix[5]phyrin for Fluoride Ion Sensing with Visible and Near Infrared Optical Responses (2018)
  • Author(s): Higashino Tomohiro、Kumagai Atsushi、Imahori Hiroshi
  • Journal Title: Chemistry - An Asian Journal Volume: 13 Issue: 16 Pages: 2019-2022
  • DOI: 10.1002/asia.201800856
  • Peer Reviewed
• [Journal Article] Reversible π-system switching of thiophene-fused thiahexaphyrins by solvent and oxidation/reduction (2018)
  • Author(s): Higashino Tomohiro、Kumagai Atsushi、Sakaki Shigeyoshi、Imahori Hiroshi
  • Journal Title: Chemical Science Volume: 9 Issue: 38 Pages: 7528-7539
  • DOI: 10.1039/c8sc02448k
  • Peer Reviewed / Open Access
• [Journal Article] Effect of Silicon Surface for Perovskite/Silicon Tandem Solar Cells: Flat or Textured? (2018)
  • Author(s): H. Kanda, N. Shibayama, A. Uzum, T. Umeyama, H. Imahori, K. Ibi, and S. Ito
  • Journal Title: ACS Appl. Mater. Interfaces Volume: 10 Issue: 41 Pages: 35016-35024
  • DOI: 10.1021/acsami.8b08701
  • Peer Reviewed
• [Journal Article] ABC-ABC-Type Directly meso-meso Linked Porphyrin Dimers (2018)
  • Author(s): Higashino Tomohiro、Kurumisawa Yuma、Iiyama Hitomi、Imahori Hiroshi
  • Journal Title: Chemistry - A European Journal Volume: 25 Issue: 2 Pages: 538-547
  • DOI: 10.1002/chem.201805405
  • Peer Reviewed
• [Journal Article] Photodynamics of Functionalized Nanocarbons: Effect of Electronic Coupling and Donor Dimerization (2018)
  • Author(s): T. Umeyama and H. Imahori
  • Journal Title: Nanoscale Horiz. Volume: 印刷中 Issue: 4 Pages: 352-366
  • DOI: 10.1039/c8nh00024g
  • Peer Reviewed / Open Access
• [Presentation] 分子工学に基づいた有機太陽電池材料の創製 (2020)
  • Author(s): 今堀博
  • Organizer: 近畿化学協会機能性色素部会第101回例会「有機太陽電池の最新動向と新展開」
  • Invited
• [Presentation] Donor-Acceptor Interactions for Energy and Biological Applications (2020)
  • 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 Conversion (2019)
  • Author(s): H. Imahori
  • Organizer: Pre-ECS Symposium
  • Int'l Joint Research / Invited
• [Presentation] Isomer Effects of Nanocarbons in Organic Solar Cells (2019)
  • 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 Donors (2019)
  • 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 Conversion (2019)
  • 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 Conversion (2019)
  • 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 Conversion (2019)
  • 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 Photovoltaics (2019)
  • 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 Photovoltaics (2019)
  • 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
• [Presentation] Molecular Engineering of Organic Photovoltaics and Solar Fuels (2019)
  • Author(s): H. Imahori
  • Organizer: 28th Inter-American Photochemcial Society (I-APS) Winter Meeting
  • Int'l Joint Research / Invited
• [Presentation] Visible Light-Driven Watern Oxidtion with Porphyrin Sensitizers and Water Oxidtion Catalysts (2018)
  • Author(s): H. Imahori
  • Organizer: 233rd Meeting of The Electrochemical Society
  • Int'l Joint Research / Invited
• [Presentation] Exciplex Formation and Decay in Porphyrin-Carbon Nanotube Ensembles (2018)
  • Author(s): H. Imahori
  • Organizer: 233rd Meeting of The Electrochemical Society
  • Int'l Joint Research / Invited
• [Presentation] Porphyrins as Excellent Sensitizers for Energy and Biological Applications (2018)
  • Author(s): H. Imahori
  • Organizer: International Conference on Porphyrins and Phthalocyanines (ICPP-10)
  • Int'l Joint Research / Invited
• [Presentation] Mimicking Photosynthesis for Photoinduced Charge Separation and Solar Energy Conversion (2018)
  • Author(s): H. Imahori
  • Organizer: The 22nd International Conference on Photochemical Conversion and Storage of Solar Energy (IPS-22)
  • Int'l Joint Research / Invited
• [Presentation] Molecular Engineering for Bulk Heterojunction and Dye-Sensitized Organic Solar Cells (2018)
  • Author(s): H. Imahori
  • Organizer: International Conference on Energy and Environmental Materials (ICEEM 2018)
  • Int'l Joint Research / Invited
• [Presentation] Porphyrins for Photoinduced Charge Separation and Solar Energy Conversion (2018)
  • Author(s): H. Imahori
  • Organizer: Asian Workshop on Frontiers of Porphyrins and Phthalocyanines
  • Int'l Joint Research / Invited
• [Presentation] Molecular Engineering for Photoinduced Charge Separation and Solar Energy Conversion (2018)
  • Author(s): H. Imahori
  • Organizer: 10th Asian Photochemistry Conference
  • Int'l Joint Research / Invited
• [Book] 未来を拓く多彩な色素材料 (2021)
  • Author(s): 今堀博（分担執筆）
  • Total Pages: 194
  • Publisher: 化学同人（日本化学会編）
  • ISBN: 9784759814002
• [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