Development of pH-controlling photoanodes for oxygen / hydrogen peroxide production toward artificial photosynthesis
| Project/Area Number |
18H02071
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Review Section |
Basic Section 36020:Energy-related chemistry
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| Research Institution | Niigata University |
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Principal Investigator |
Yagi Masayuki 新潟大学, 自然科学系, 教授 (00282971)
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| Project Period (FY) |
2018-04-01 – 2021-03-31
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| Project Status |
Completed (Fiscal Year 2020)
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| Budget Amount *help |
¥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)
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| 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 |
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| 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.
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| 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。
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Report
(4 results)
Research Products
(36 results)
