分子性触媒コンポーネントを融合させた太陽光水分解用光電気化学セルの開発

• Project Area: Creation of novel light energy conversion system through elucidation of the molecular mechanism of photosynthesis and its artificial design in terms of time and space
• Project/Area Number: 18H05171
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Research Institution: Kyushu University
• Principal Investigator: 酒井 健 九州大学, 理学研究院, 教授 (30235105)
• Project Period (FY): 2018-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000); Fiscal Year 2019: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000); Fiscal Year 2018: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
• Keywords: 太陽光水分解 / 分子性触媒 / 光増感剤 / 光電気化学 / 水分解 / 光電気化学セル / 錯体触媒 / 錯体色素 / 起電力 / フェルミ準位 / 分子性色素

Outline of Annual Research Achievements

昨年度は、ノンバイアスでの光化学的な水の完全分解を駆動する分子性光電気化学セルの開発に向けた第一歩として、電気化学的な水の完全分解(水を2:1のモル比で水素と酸素に分解する反応)を駆動する分子性電気化学セルの開発に取り組んだ。白金ポルフィリン水素生成触媒を修飾したTiO2電極(FTO/TiO2/PtP-py電極)をアノード、コバルトポルフィリン酸素生成触媒を修飾したTiO2電極(FTO/TiO2/CoP-py電極)をカソードとして用いた分子性電気化学セルにおいて、両極間に2.2 Vの電圧を印加すると、水の完全分解が効率良く進行し、そのファラデー効率は非常に高いことが明らかとなった。本分子性電気化学セルは、分子性触媒修飾電極を用いて水の完全分解に成功した初めて例であり、本研究課題の目的達成に向けた重要な成果となっている。
今年度は、水からの光化学的酸素生成触媒機能を示す酸素生成フォトアノードの開発に取り組んだ。酸素生成フォトアノードに用いる各種錯体色素、および錯体触媒の合成を行い、これらを共吸着させたTiO2電極(酸素生成フォトアノード)の作製を試みた。様々な吸着方法を検討した結果、錯体色素と錯体触媒をTiO2電極に逐次的に吸着させることによって、酸素生成フォトアノードを作製できることが明らかとなった。作製した酸素生成フォトアノードの電気化学特性を詳細に検討したところ、期待通り、可視光照射下において水からの酸素生成触媒反応を駆動可能であることが明らかとなった。今年度は、COVID-19による数ヶ月間の大学閉鎖の影響によって、本酸素生成フォトアノードを用いた分子性光電気化学セルによる水の完全分解反応に関する検討を行なうことはできなかったが、本研究課題の目的達成に向けて重要な成果をあげることが出来たと言える。

Research Progress Status

令和元年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和元年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Unexpected structure of enaminone Pd(II) complex in comparison with Cu(II) complex: Synthesis, characterization, DNA binding and antitumor activity (2021)
  • Author(s): El-Ghamry Hoda A.、Yamauchi Kosei、Sakai Ken、Farghaly Thoraya A.
  • Journal Title: Inorganica Chimica Acta Volume: 516 Pages: 120117-120117
  • DOI: 10.1016/j.ica.2020.120117
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Improving the overall performance of photochemical H2 evolution catalyzed by the Co-NHC complex via the redox tuning of electron relays (2021)
  • Author(s): Yatsuzuka Koichi、Yamauchi Kosei、Kawano Ken、Ozawa Hironobu、Sakai Ken
  • Journal Title: Sustainable Energy & Fuels Volume: 5 Issue: 3 Pages: 740-749
  • DOI: 10.1039/d0se01597k
  • Peer Reviewed
• [Journal Article] A dinuclear nickel catalyst based on metal-metal cooperation for electrochemical hydrogen production (2020)
  • Author(s): Hamaguchi Tomohiko、Kai Keisuke、Ando Isao、Kawano Ken、Yamauchi Kosei、Sakai Ken
  • Journal Title: Inorganica Chimica Acta Volume: 505 Pages: 119498-119498
  • DOI: 10.1016/j.ica.2020.119498
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] A Molecular-Based Water Electrolyzer Consisting of Two Mesoporous TiO2 Electrodes Modified with Metalloporphyrin Molecular Catalysts Showing a Quantitative Faradaic Efficiency (2020)
  • Author(s): Akamine Katsuhiro、Morita Kohei、Sakai Ken、Ozawa Hironobu
  • Journal Title: ACS Applied Energy Materials Volume: 3 Issue: 5 Pages: 4860-4866
  • DOI: 10.1021/acsaem.0c00443
  • Peer Reviewed
• [Journal Article] Highly Efficient and Selective Photocatalytic CO2 Reduction to CO in Water by a Cobalt Porphyrin Molecular Catalyst (2019)
  • Author(s): Call Arnau、Cibian Mihaela、Yamamoto Keiya、Nakazono Takashi、Yamauchi Kosei、Sakai Ken
  • Journal Title: ACS Catalysis Volume: 9 Issue: 6 Pages: 4867-4874
  • DOI: 10.1021/acscatal.8b04975
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Mechanisms of water oxidation using ruthenium, cobalt, copper, and iron molecular catalysts (2019)
  • Author(s): Parent Alexander Rene、Nakazono Takashi、Tsubonouchi Yuta、Taira Natsuki、Sakai Ken
  • Journal Title: Advances in Inorganic Chemistry Volume: 74 Pages: 197-240
  • DOI: 10.1016/bs.adioch.2019.04.001
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Room-Temperature Benzylic Alkylation of Benzylic Carbonates: Improvement of Palladium Catalyst and Mechanistic Study (2019)
  • Author(s): Kuwano Ryoichi、Yokogi Masashi、Sakai Ken、Masaoka Shigeyuki、Miura Takashi、Won Sungyong
  • Journal Title: Organic Process Research & Development Volume: 23 Issue: 8 Pages: 1568-1579
  • DOI: 10.1021/acs.oprd.9b00210
  • Peer Reviewed
• [Journal Article] A Molecular Cobalt Hydrogen Evolution Catalyst Showing High Activity and Outstanding Tolerance to CO and O2 (2019)
  • Author(s): Wang Jia‐Wei、Yamauchi Kosei、Huang Hai‐Hua、Sun Jia‐Kai、Luo Zhi‐Mei、Zhong Di‐Chang、Lu Tong‐Bu、Sakai Ken
  • Journal Title: Angewandte Chemie International Edition Volume: 58 Issue: 32 Pages: 10923-10927
  • DOI: 10.1002/anie.201904578
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] An earth-abundant system for light-driven CO2 reduction to CO using a pyridinophane iron catalyst (2019)
  • Author(s): Sakaguchi Yuto、Call Arnau、Cibian Mihaela、Yamauchi Kosei、Sakai Ken
  • Journal Title: Chemical Communications Volume: 55 Issue: 59 Pages: 8552-8555
  • DOI: 10.1039/c9cc04191e
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Photochemical CO2 Reduction Driven by Water-Soluble Copper(I) Photosensitizer with the Catalysis Accelerated by Multi-Electron Chargeable Cobalt Porphyrin (2019)
  • Author(s): Zhang Xian、Cibian Mihaela、Call Arnau、Yamauchi Kosei、Sakai Ken
  • Journal Title: ACS Catalysis Volume: 9 Issue: 12 Pages: 11263-11273
  • DOI: 10.1021/acscatal.9b04023
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Consecutive ligand-based PCET processes affording a doubly reduced nickel pyrazinedithiolate which transforms into a metal hydride required to evolve H2 (2019)
  • Author(s): Koshiba Keita、Yamauchi Kosei、Sakai Ken
  • Journal Title: Dalton Transactions Volume: 48 Issue: 2 Pages: 635-640
  • DOI: 10.1039/c8dt04497j
  • Peer Reviewed
• [Journal Article] A New Class of Molecular-Based Photoelectrochemical Cell for Solar Hydrogen Production Consisting of Two Mesoporous TiO2 Electrodes (2019)
  • Author(s): Morita Kohei, Sakai Ken, and Ozawa Hironobu
  • Journal Title: ACS Applied Energy Materials Volume: 2 Issue: 2 Pages: 987-992
  • DOI: 10.1021/acsaem.8b01992
  • Peer Reviewed
• [Journal Article] Ligand‐based PCET Reduction in a Heteroleptic Ni(bpy)(dithiolene) Electrocatalyst Giving Rise to Higher Metal Basicity Required for Hydrogen Evolution (2019)
  • Author(s): Koshiba Keita、Yamauchi Kosei、Sakai Ken
  • Journal Title: ChemElectroChem Volume: － Issue: 8 Pages: 2273-2281
  • DOI: 10.1002/celc.201900400
  • Peer Reviewed
• [Journal Article] Photocatalytic H2 Evolution Using a Ru Chromophore Tethered to Six Viologen Acceptors (2018)
  • Author(s): Yamamoto Keiya, Call Arnau, and Sakai Ken
  • Journal Title: Chemistry - A European Journal Volume: 24 Issue: 62 Pages: 16620-16629
  • DOI: 10.1002/chem.201803662
  • Peer Reviewed
• [Journal Article] A family of molecular nickel hydrogen evolution catalysts providing tunable overpotentials using ligand-centered proton-coupled electron transfer paths (2018)
  • Author(s): Aimoto Yutaro、Koshiba Keita、Yamauchi Kosei、Sakai Ken
  • Journal Title: Chemical Communications Volume: 54 Issue: 91 Pages: 12820-12823
  • DOI: 10.1039/c8cc07467d
  • Peer Reviewed
• [Presentation] Molecular-Based Photoelectrochemical Cell for Solar Hydrogen Production Consisting of Two TiO2 electrodes (2019)
  • Author(s): Hironobu Ozawa
  • Organizer: International Conference on Photocatalysis and Photoenergy
  • Int'l Joint Research / Invited
• [Presentation] Molecular Catalysts Promoting Hydrogen Evolution from Water via Unique Proton-coupled Electron Transfer Processes (2019)
  • Author(s): Kosei Yamauchi,
  • Organizer: The 23rd International Symposium on the Photochemistry and Photophysics of Coordination Compounds (ISPPCC2019)
  • Int'l Joint Research
• [Presentation] Kinetics and DFT Studies of Water Oxidation Catalyzed by a Monocobalt Polyoxometalate (2019)
  • Author(s): Natsuki Taira, Kosei Yamauch, Ken Sakai
  • Organizer: The 23rd International Symposium on the Photochemistry and Photophysics of Coordination Compounds (ISPPCC2019)
  • Int'l Joint Research
• [Presentation] Molecular Catalysis Relevant to Solar Energy Conversion and Storage (2019)
  • Author(s): Ken Sakai
  • Organizer: The 23rd International Symposium on the Photochemistry and Photophysics of Coordination Compounds (ISPPCC2019)
  • Int'l Joint Research / Invited
• [Presentation] Molecular-Based Photoelectrochemical Cell for Solar Hydrogen Production Consisting of Two TiO2 electrodes (2019)
  • Author(s): Hironobu Ozawa
  • Organizer: The 23rd International Symposium on the Photochemistry and Photophysics of Coordination Compounds (ISPPCC2019)
  • Int'l Joint Research
• [Presentation] 分子性触媒を修飾したTiO2電極を両極に用いた 電気化学セルによる低過電圧水分解 (2019)
  • Author(s): Hironobu Ozawa
  • Organizer: 新学術領域研究I4LEC個別班会議、第2回合同班会議
• [Presentation] Molecular Catalysis Towards Artificial Solar Generation of Fuels (2019)
  • Author(s): Ken Sakai
  • Organizer: 19th International Conference on Biological Inorganic Chemistry (ICBIC-19)
  • Int'l Joint Research / Invited
• [Presentation] Molecular Photocatalysis Towards Solar Water Splitting and CO2 Reduction (2019)
  • Author(s): Ken Sakai
  • Organizer: 2019 ESP-IUPB World Congress
  • Int'l Joint Research / Invited
• [Presentation] 分子性光電気化学セルによる太陽光水分解 (2019)
  • Author(s): Hironobu Ozawa
  • Organizer: 新学術領域研究I4LEC個別班会議
• [Presentation] Molecular Catalysis for Water Splitting and CO2 Reduction (2019)
  • Author(s): Ken Sakai
  • Organizer: 7th Asian Conference on Coordination Chemistry (ACCC7)
  • Int'l Joint Research / Invited
• [Presentation] Molecular Catalysis and Photocatalysis for Water Splitting and CO2 Reduction (2019)
  • Author(s): Ken Sakai
  • Organizer: 12th China-Japan Joint Symposium on metal Cluster Compounds (CJJSMCC2019)
  • Int'l Joint Research / Invited
• [Presentation] A Cu-based Photosensitizer with Cobaltoporphyrin Catalyst for Efficient Photocatalytic CO2 Reduction in Fully Aqueous Media (2019)
  • Author(s): Xian Zhang
  • Organizer: 12th China-Japan Joint Symposium on metal Cluster Compounds (CJJSMCC2019)
  • Int'l Joint Research
• [Presentation] Molecular Catalysis and Photocatalysis for Water Splitting and CO2 Reduction (2019)
  • Author(s): Ken Sakai
  • Organizer: International Conference on Artificial Photosynthesis-2019 (ICARP2019)
  • Int'l Joint Research / Invited
• [Presentation] 分子性触媒コンポーネントを融合させた太陽光水分解用光電気化学セルの開発 (2019)
  • Author(s): Hironobu Ozawa
  • Organizer: I4LEC第２回班会議、第２回公開シンポジウム
  • Invited
• [Presentation] 低過電圧水素生成錯体触媒の開発と反応機構解析 (2019)
  • Author(s): Yutaro Aimoto, Kosei Yamamoto, and Ken Sakai
  • Organizer: I4LEC第２回班会議、第２回公開シンポジウム
• [Presentation] ジアザピリジノファン配位子を有する第一遷移金属錯体を用いた光化学的二酸化炭素還元反応 (2019)
  • Author(s): Yuto Sakaguchi, Mihaela Cibian, Arnau Call, and Ken Sakai
  • Organizer: 日本化学会第99春季年会
• [Presentation] 分子性色素増感光電気化学セルによる太陽光水分解 (2019)
  • Author(s): Hironobu Ozawa
  • Organizer: 日本化学会第99春季年会
  • Invited
• [Presentation] コバルト単核活性部位を有するポリオキソメタレート錯体触媒の 酸素発生反応機構解析 (2019)
  • Author(s): Natsuki Taira, Kosei Yamauchi, and Ken Sakai
  • Organizer: 日本化学会第99春季年会
• [Presentation] Molecular Catalysts and Photocatalysts for Water Splitting Reactions and their Applications in Surface Modified TiO2 Electrodes (2018)
  • Author(s): Ken Sakai
  • Organizer: I2CNER-UGo, IRTG Proposal Workshop
  • Int'l Joint Research / Invited
• [Presentation] Hybrid Molecular Catalysts and Photocatalysts for Solar Water Splitting Reactions (2018)
  • Author(s): Ken Sakai
  • Organizer: 3rd Japan - UK Joint Symposium on Coordination Chemistry
  • Int'l Joint Research / Invited
• [Presentation] Catalytic Hydrogen Evolution Reactions Coupled with Proton-Coupled Electron Transfer Processes (2018)
  • Author(s): Ken Sakai
  • Organizer: 3rd International Conference on Proton Coupled Electron Transfer (PCET2018)
  • Int'l Joint Research / Invited
• [Presentation] Water Oxidation and CO2 Reduction Catalyzed by Co-, Cu- and Ru-Centered Catalysts including Cobalt Porphyrins (2018)
  • Author(s): Ken Sakai
  • Organizer: Tenth International Conference on Porphyrins and Phthalocyanines(ICPP-10)
  • Int'l Joint Research / Invited
• [Presentation] Coordination Chemistry focused on Photochemical Water Splitting Molecular Devices (2018)
  • Author(s): Ken Sakai
  • Organizer: 43rd International Conference on Coordination Chemistry(ICCC2018)
  • Int'l Joint Research / Invited
• [Presentation] Catalysis of metals and metal complexes (2018)
  • Author(s): Ken Sakai
  • Organizer: Summer Shool 2018 on Young Coordination Chemist's Association Japan
  • Invited
• [Presentation] Solar Energy Conversion and Storage using Transition Metal Molecular Systems (2018)
  • Author(s): Ken Sakai
  • Organizer: CSOM Workshop
  • Int'l Joint Research / Invited
• [Presentation] Molecular Catalysts and Photocatalysts towards Artificial Photosynthesis (2018)
  • Author(s): Ken Sakai
  • Organizer: Department Seminar at School of Science, The University of Tokyo
  • Invited
• [Presentation] Molecular Catalysts and Photocatalysts for Solar Energy Conversion and Storage (2018)
  • Author(s): Ken Sakai
  • Organizer: 2nd Kyushu-Mainz Joint Chemistry Symposium
  • Int'l Joint Research / Invited
• [Presentation] 分子性触媒コンポーネントを融合させた太陽光水分解用光電気化学セルの開発 (2018)
  • Author(s): Ken Sakai
  • Organizer: I4LEC第1回合同班会議
  • Invited
• [Presentation] Mechanistic Studies on Water oxidation Catalyzed by Cobalt Polyoxometalates with Stopped-flow Techniques (2018)
  • Author(s): Natsuki Taira, Yuta Tsubonouchi, Kosei Yamauchi, and Ken Sakai
  • Organizer: 43rd International Conference on Coordination Chemistry(ICCC2018)
  • Int'l Joint Research
• [Presentation] Near-Infrared Light-Driven Hydrogen Evolution Photosensitized by a Polypyridyl Triruthenium Photosensitizer (2018)
  • Author(s): Yutaro Tsuji, Kosei Yamauchi, and Ken Sakai
  • Organizer: 43rd International Conference on Coordination Chemistry(ICCC2018)
  • Int'l Joint Research
• [Presentation] Synthesis and H2-evolving Activity of New Dinuclear Platinum(Ⅱ) Bipyridine Complexes Having an Intramolecular Metal -Metal Interaction (2018)
  • Author(s): Kazuma Yamakawa, Fumiaki Wakiyama, Kosei Yamauchi, and Ken Sakai
  • Organizer: 43rd International Conference on Coordination Chemistry(ICCC2018)
  • Int'l Joint Research
• [Presentation] 分子性触媒コンポーネントを融合させた太陽光水分解用光電気化学セルの開発 (2018)
  • Author(s): Toshihiro Koga, Kosei Yamauchi, and Ken Sakai
  • Organizer: 錯体化学若手の会夏の学校2018
• [Book] 光エネルギー変換における分子触媒の新展開 9章 分子性色素増感光電気化学セルによる太陽光水分解 (2020)
  • Author(s): 森田浩平、酒井 健、小澤弘宜
  • Total Pages: 9
  • Publisher: 化学同人
  • ISBN: 9784759813982
• [Book] エネルギー・資源 特集 人工光合成研究の最前線(5) 分子性錯体触媒を修飾したTiO2電極による水の完全分解 (2020)
  • Author(s): 小澤弘宜、酒井 健
  • Total Pages: 6
  • Publisher: エネルギー・資源学会
• [Remarks] 九州大学大学院理学研究院化学部門 錯体化学研究室 酒井・小澤グループ
  • URL: http://www.scc.kyushu-u.ac.jp/Sakutai/jp/index.html