| Project/Area Number |
24655044
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| Research Category |
Grant-in-Aid for Challenging Exploratory Research
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| Allocation Type | Single-year Grants |
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| Research Field |
Inorganic chemistry
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| Research Institution | University of Tsukuba |
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Principal Investigator |
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| Co-Investigator(Renkei-kenkyūsha) |
ISHIZUKA Tomoya 筑波大学, 数理物質系, 講師 (20435522)
KOTANI Hiroaki 筑波大学, 数理物質系, 助教 (10610743)
FUKUZUMI Shunichi 大阪大学, 工学研究科, 教授 (40144430)
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| Project Period (FY) |
2012-04-01 – 2014-03-31
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| Project Status |
Completed (Fiscal Year 2013)
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| Budget Amount *help |
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2013: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Fiscal Year 2012: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
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| Keywords | 触媒・化学プロセス / 再生可能エネルギー / コバルト錯体 / 水の酸化反応 / プロトン共役電子移動 |
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| Research Abstract |
We succeeded in catalytic water oxidation using a bis-mu-hydroxo-Co(III)-TPA dimer complex, [CoIII(mu-OH)(TPA)]2(ClO4)4 (1) (TPA = tris(2-pyridylmethyl)amine), as a catalyst. We conducted the catalytic oxidation with a chemical oxidant, [Ru(bpy)3]3+, to observe O2 evolution and excellent stability of 1 under catalytic conditions. Based on detailed electrochemical and isotope-labeling studies, we proposed a plausible reaction mechanism of the catalytic water oxidation by complex 1, where the oxidation process of the two Co(III) centers to give a bis-mu-oxyl dinuclear Co(III) species is the rate-determining step and intramolecular O-O bond formation in the intermediate. Furthermore, we applied the system to photocatalytic water oxidation using a Ru-based photosensitizer and persulfate as an oxidant in borate buffer at pH 9.3. We obtained the maximum TON of the photocatalysis to be 742, together with the highest quantum yield of 88%, for the dioxygen production.
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