Development of pH-controlling photoanodes for oxygen / hydrogen peroxide production toward artificial photosynthesis

• Project/Area Number: 18H02071
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 36020:Energy-related chemistry
• Research Institution: Niigata University
• Principal Investigator: Yagi Masayuki 新潟大学, 自然科学系, 教授 (00282971)
• Project Period (FY): 2018-04-01 – 2021-03-31
• Project Status: Completed (Fiscal Year 2020)
• Budget Amount: ¥17,160,000 (Direct Cost: ¥13,200,000、Indirect Cost: ¥3,960,000); Fiscal Year 2020: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000); Fiscal Year 2019: ¥5,590,000 (Direct Cost: ¥4,300,000、Indirect Cost: ¥1,290,000); Fiscal Year 2018: ¥6,110,000 (Direct Cost: ¥4,700,000、Indirect Cost: ¥1,410,000)
• Keywords: 水の酸化触媒 / 酸素発生 / 光合成 / 人工光合成 / 二核ルテニウム錯体 / O-O結合形成機構 / O-O結合形成 / 酸素発生触媒 / ルテニウム錯体 / 水の酸化アノード / 水の酸化 / 過酸化水素生成 / 水の酸化光アノード

Outline of Final Research Achievements

The understanding of O-O bond formation is of great importance for revealing the mechanism of water oxidation in photosynthesis and for developing efficient catalysts for water oxidation in artificial photosynthesis. The chemical oxidation of the RuII2(OH)(OH2) core with the vicinal OH and OH2 ligands was spectroscopically and theoretically investigated to provide a mechanistic insight into the O-O bond formation in the core. We demonstrate the first O-O bond formation at the low-valent RuIII2(OH) core with the vicinal OH ligands to form the RuII2(μ-OOH) core with a μ-OOH bridge. The O-O bond formation is induced by deprotonation of one of the OH ligands of RuIII2(OH)2 via intramolecular coupling of the OH and deprotonated O- ligands, conjugated with 2-electron transfer from two RuIII centers to their ligands. The intersystem crossing between singlet and triple states of RuII2(μ-OOH) is easily switched by exchange of H+ between the μ-OOH bridge and the auxiliary back bone ligand.

Academic Significance and Societal Importance of the Research Achievements

光合成の分野において、酸素発生錯体（OEC)での、O-O結合形成機構の理解は、重要な研究課題である。一方、次世代のエネルギー供給システムとして期待されている人工合成の構築では、高活性な酸素発生触媒の開発が大きな足かせとなっている。酸素発生のためのO-O結合形成の理解は、高活性触媒開発に重要である。本研究では、二核ルテニウム錯体のOH-配位子のプロトンの解離により、2つのRu3+-OH間の分子内カップリングが誘起され、O-O結合が形成されることを実証した。これは低原子価Ru3+でO-O結合形成が観察された世界初の例である。

Research Products

• [Journal Article] Concisely Synthesized FeNiWOx Film as a Highly Efficient and Robust Catalyst for Electrochemical Water Oxidation (2021)
  • Author(s): Zahran Zaki N.、Mohamed Eman A.、Tsubonouchi Yuta、Ishizaki Manabu、Togashi Takanari、Kurihara Masato、Saito Kenji、Yui Tatsuto、Yagi Masayuki
  • Journal Title: ACS Applied Energy Materials Volume: 4 Issue: 2 Pages: 1410-1420
  • DOI: 10.1021/acsaem.0c02628
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Multi-potential-step chronocoulospectrometry for electrocatalytic water oxidation by a mononuclear ruthenium aquo complex immobilized on a mesoporous ITO electrode (2020)
  • Author(s): Yuta Tsubonouchi, Junichiro Honta, Taisei Sato, Eman A. Mohamed, Zaki N. Zahran, Kenji Saito, Tatsuto Yui, and Masayuki Yagi
  • Journal Title: Dalton Trans. Volume: 49 Issue: 5 Pages: 1416-1423
  • DOI: 10.1039/c9dt04442f
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Highly Efficient and Selective Electrocatalytic CO2-to-CO Conversion by a Non-heme Iron Complex with an In-Plane N4 Ligand in Heterogeneous Aqueous Media (2020)
  • Author(s): Mohamed Eman A.、Zahran Zaki N.、Tsubonouchi Yuta、Saito Kenji、Yui Tatsuto、Yagi Masayuki
  • Journal Title: ACS Applied Energy Materials Volume: 3 Issue: 5 Pages: 4114-4120
  • DOI: 10.1021/acsaem.9b02548
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Molecular aspects, electrochemical properties and water oxidation catalysis on a nanoporous TiO2 electrode anchoring a mononuclear ruthenium(II) aquo complex (2020)
  • Author(s): Tsubonouchi Yuta、Eo Tatsuya、Honta Junichiro、Sato Taisei、Mohamed Eman A.、Zahran Zaki N.、Saito Kenji、Yui Tatsuto、Yagi Masayuki
  • Journal Title: Journal of Photochemistry and Photobiology A: Chemistry Volume: in press Pages: 112696-112696
  • DOI: 10.1016/j.jphotochem.2020.112696
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] A multi-stimuli responsive ruthenium complex for catalytic water oxidation (2020)
  • Author(s): Hirahara Masanari、Goto Hiroki、Yagi Masayuki、Umemura Yasushi
  • Journal Title: Chemical Communications Volume: 56 Issue: 84 Pages: 12825-12828
  • DOI: 10.1039/d0cc04940a
  • Peer Reviewed
• [Journal Article] Efficient Electrocatalytic Water Oxidation by a Dinuclear Ruthenium(II) Complex with Vicinal Aquo and Hydroxo Groups Adsorbed on a TiO2 Electrode (2020)
  • Author(s): Tanahashi Yuki、Nagai Sho、Tsubonouchi Yuta、Hirahara Masanari、Sato Taisei、Mohamed Eman A.、Zahran Zaki N.、Saito Kenji、Yui Tatsuto、Yagi Masayuki
  • Journal Title: ACS Applied Energy Materials Volume: 3 Issue: 12 Pages: 12172-12184
  • DOI: 10.1021/acsaem.0c02242
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] High Potential-Applied Catalyst Behavior of a Mononuclear Ruthenium(II) Complex on a Mesoporous ITO Electrode for Water Oxidation (2020)
  • Author(s): Tsubonouchi Yuta、Tanahashi Yuki、Eo Tatsuya、Honta Junichiro、Sato Taisei、Mohamed Eman A.、Zahran Zaki N.、Saito Kenji、Yui Tatsuto、Yagi Masayuki
  • Journal Title: Journal of The Electrochemical Society Volume: 167 Issue: 16 Pages: 166515-166515
  • DOI: 10.1149/1945-7111/abd3ba
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Photoisomerization and thermal isomerization of ruthenium aqua complexes with chloro-substituted asymmetric bidentate ligands (2019)
  • Author(s): M. Hirahara, H. Goto, Rei. Yamamoto, M. Yagi, and Y. Umemura
  • Journal Title: RSC Advances Volume: 9 Issue: 4 Pages: 2002-2010
  • DOI: 10.1039/c8ra08943d
  • Peer Reviewed / Open Access
• [Journal Article] Critical Hammett Electron-Donating Ability of Substituent Groups for Efficient Water Oxidation Catalysis by Mononuclear Ruthenium Aquo Complexes (2019)
  • Author(s): Watabe Shunsuke、Tanahashi Yuki、Hirahara Masanari、Yamazaki Hirosato、Takahashi Kosuke、Mohamed Eman A.、Tsubonouchi Yuta、Zahran Zaki N.、Saito Kenji、Yui Tatsuto、Yagi Masayuki
  • Journal Title: Inorganic Chemistry Volume: 58 Issue: 19 Pages: 12716-12723
  • DOI: 10.1021/acs.inorgchem.9b01623
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Facile and sustainable fabrication of transparent mesoporous IrOx films formed by nanoparticle assembly for efficient electrocatalytic water oxidation (2019)
  • Author(s): Chandra Debraj、Sato Tsubasa、Abe Naoto、Saito Kenji、Yui Tatsuto、Yagi Masayuki
  • Journal Title: Sustainable Energy & Fuels Volume: 3 Issue: 12 Pages: 3489-3497
  • DOI: 10.1039/c9se00731h
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Characterization and Mechanism of Efficient Visible-Light-Driven Water Oxidation on an in Situ N2-Intercalated WO3 Nanorod Photoanode (2019)
  • Author(s): Chandra Debraj、Li Dong、Sato Tetsuya、Tanahashi Yuki、Togashi Takanari、Ishizaki Manabu、Kurihara Masato、Mohamed Eman A.、Tsubonouchi Yuta、Zahran Zaki N.、Saito Kenji、Yui Tatsuto、Yagi Masayuki
  • Journal Title: ACS Sustainable Chemistry & Engineering Volume: 7 Issue: 21 Pages: 17896-17906
  • DOI: 10.1021/acssuschemeng.9b04467
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Facile fabrication and nanostructure control of mesoporous iridium oxide films for efficient electrocatalytic water oxidation (2019)
  • Author(s): D. Chandra, T. Sato, Y. Tanahashi, R. Takeuchi, M. Yagi,
  • Journal Title: Energy Volume: 173 Pages: 278-289
  • DOI: 10.1016/j.energy.2019.02.072
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Recent Advances in the Development of Molecular Catalyst‐Based Anodes for Water Oxidation toward Artificial Photosynthesis (2019)
  • Author(s): Zaki N. Zahran, Yuta Tsubonouch, Eman A. Mohamed, Masayuki Yagi
  • Journal Title: ChemSusChem Volume: 12 Issue: 9 Pages: 1775-1793
  • DOI: 10.1002/cssc.201802795
  • Peer Reviewed / Int'l Joint Research
• [Presentation] 歪んだ構造を有する高活性酸素発生錯体モデル (2020)
  • Author(s): 榮治 雅弘、坪ノ内 優太、園川大樹、平原将也、モハメド エマン、ザハラン ザキ、齋藤 健二、由井 樹人、八木 政行
  • Organizer: 錯体化学会第70回討論会
• [Presentation] 高活性酸素発生触媒開発に向けた二核ルテニウムアコ錯体群のone-pot光異性化戦略 (2020)
  • Author(s): 吉田万葉、金子慶太朗、佐藤大成、モハメド エマン、坪ノ内優太、ザハラン ザキ、齊藤健二、由井樹人、八木政行
  • Organizer: 日本化学会第100春季年会
• [Presentation] BiVO4光アノードの簡便合成と高効率可視光駆動酸素発生反応 (2020)
  • Author(s): 江尾達矢、佐藤大成、モハメド エマン、坪ノ内優太、ザハラン ザキ、齊藤健二、由井樹人、八木政行
  • Organizer: 日本化学会第100春季年会
• [Presentation] Fe(III)イオンの錯形成反応を用いて合成したα-Fe2O3光アノードによる高効率可視光駆動酸素発生反応 (2020)
  • Author(s): 勝木友洋、佐藤大成、モハメド エマン、坪ノ内優太、ザハラン ザキ、齊藤健二、由井樹人、八木政行
  • Organizer: 日本化学会第100春季年会
• [Presentation] 高平面型N4配位子鉄錯体修飾多孔性金属電極による高効率水の酸化触媒反応 (2020)
  • Author(s): 早坂太智、佐藤大成、坪ノ内優太、モハメド エマン、ザハラン ザキ、齊藤健二、由井樹人、八木政行
  • Organizer: 日本化学会第100春季年会
• [Presentation] Mechanisms of pH-dependent activity for water oxidation by dinuclear ruthenium catalysts on carbon electrodes (2020)
  • Author(s): Yuta Tsubonouchi, Taichi Hayasaka, Yuki Wakai, Taisei Sato, Eman A. Mohamed, Zaki N. Zahran, Kenji Saito, Yui Tatsuto, Masayuki Yag
  • Organizer: 日本化学会第100春季年会
• [Presentation] New development of efficient catalyst for water splitting (2019)
  • Author(s): Masayuki Yagi
  • Organizer: International Conference on Photocatalysis and Photoenergy 2019 (ICOPP2019)
  • Int'l Joint Research / Invited
• [Presentation] C1 化学触媒システムのための酸素発生電極触媒 (2019)
  • Author(s): Masayuki Yagi
  • Organizer: ゼロエミッションを目指したC1 化学触媒システム開発研究会
  • Invited
• [Presentation] 酸素発生電極触媒の現状と新展開 (2019)
  • Author(s): Masayuki Yagi
  • Organizer: 光機能材料研究会第７４回講演会、「電極触媒によるエネルギー変換と有用化学品製造」
  • Invited
• [Presentation] A highly efficient transparent water oxidation catalyst toward artificial photosynthesis (2019)
  • Author(s): Masayuki Yagi
  • Organizer: 3rd International Solar Fuels Conference (ISF-3) and International Conference on Artificial Photosynthesis-2019 (ICARP2019)
  • Int'l Joint Research / Invited
• [Presentation] Immobilization of a Molecular Ruthenium Catalyst on Carbon Electrodes for Efficient and Stable Electrochemical Water Oxidation (2019)
  • Author(s): Yuta Tsubonouchi, Taichi Hayasaka, Yuki Wakai, Eman A. Mohamed, Zaki N. Zahran, Kenji Saito, Yui Tatsuto, Masayuki Yagi
  • Organizer: 3rd International Solar Fuels Conference (ISF-3) and International Conference on Artificial Photosynthesis-2019 (ICARP2019)
  • Int'l Joint Research
• [Presentation] Oxides, phosphides, and sulfides of mixed iron/nickel/tungsten as bifunctional water splitting catalysts (2019)
  • Author(s): Zaki. N. Zahran, Eman A. Mohamed, Yuta Tsubonouchi, Kenji Saito, Tatsuto Yui and Masayuki Yagi
  • Organizer: 3rd International Solar Fuels Conference (ISF-3) and International Conference on Artificial Photosynthesis-2019 (ICARP2019)
  • Int'l Joint Research
• [Presentation] Highly efficient transparent water oxidation catalysts toward artificial photosynthesis (2019)
  • Author(s): Masayuki Yagi
  • Organizer: The Second International Conference of Polymeric and Organic Materials in Yamagata University (IPOMY)
  • Int'l Joint Research / Invited
• [Presentation] ナノ構造制御された酸化タングステンの光・電子機能 (2019)
  • Author(s): 八木 政行
  • Organizer: 第31回配位化合物の光化学討論会
• [Presentation] 光透過性混合金属酸化物の低過電圧酸素発生 (2019)
  • Author(s): ザフラン ザキ，モハマド エマン，坪ノ内優太，齊藤健二，由井 樹人，八木政行
  • Organizer: 2019年電気化学秋季大会
• [Presentation] 水の酸化光触媒活性に及ぼすナノワイヤーおよび六角柱酸化タングステンの臨界転移効果 (2019)
  • Author(s): 曽根 和哉、立垣 優子、佐藤 太哉、棚橋 祐樹、モハマド エマン、坪ノ内 優太、ザハラン ザキ、齊藤 健二、由井 樹人、八木 政行
  • Organizer: 2019 年光化学討論会
• [Presentation] 二核ルテニウム錯体の不可逆的架橋変換と水の酸化触媒活性に及ぼすその影響 (2019)
  • Author(s): 園川 大樹、坪ノ内 優太、モハメド エマン、ザハラン ザキ、齋藤 健二、由井 樹人、八木 政行
  • Organizer: 錯体化学会第69回討論会
• [Presentation] Remarkably stable electrocatalysis for water oxidation by a dinuclear ruthenium complex immobilized on carbon electrodes (2019)
  • Author(s): Yuta Tsubonouchi, Taichi Hayasaka, Yuki Wakai, Eman A. Mohamed, Zaki N. Zahran, Kenji Saito, Yui Tatsuto, Masayuki Yagi
  • Organizer: 錯体化学会第69回討論会
• [Presentation] Physicochemical properties and thermal isomerization of homoleptic ruthenium complexes with asymmetric ligands (2019)
  • Author(s): Yuta Tsubonouchi, Hiroki Sonokawa, Kenji Saito, Tatsuto Yui, Tsubasa Hatanaka, Yasuhiro Funahashi, Koichi Nozaki, Masayuki Yagi
  • Organizer: 日本化学会第99春季年会
• [Presentation] Electrochemical water oxidation catalyzed by a dinuclear ruthenium complex having a carboxylate-anthyridine ligand (2019)
  • Author(s): Hiroki Sonokawa, Yuta Tsubonouchi, Kenji Saito, Tatsuto Yui, Masayuki Yagi
  • Organizer: 日本化学会第99春季年会
• [Presentation] 共役大環状配位子を有する卑金属錯体の合成と酸素発生触媒機能 (2019)
  • Author(s): 高橋 大生、坪ノ内 優太、齊藤 健二、由井 樹人、八木 政行
  • Organizer: 日本化学会第99春季年会
• [Book] Photoisomerization: Causes, Behavior and Effects (2019)
  • Author(s): Y. Tanahashi, S. Watabe, E. A. Mohamed, Y. Tsubonouchi, Z. N. Zahran, M. Hirahara, M. Yagi
  • Total Pages: 29
  • Publisher: Nova Science Publishers
  • ISBN: 9781536153132
• [Book] 錯体化合物辞典 (2019)
  • Author(s): 八木政行
  • Total Pages: 1
  • Publisher: 朝倉書店