| Project/Area Number |
15K17834
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| Research Category |
Grant-in-Aid for Young Scientists (B)
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| Allocation Type | Multi-year Fund |
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| Research Field |
Inorganic chemistry
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| Research Institution | Chuo University |
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Principal Investigator |
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| Project Period (FY) |
2015-04-01 – 2017-03-31
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| Project Status |
Completed (Fiscal Year 2016)
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| Budget Amount *help |
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2016: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2015: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
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| Keywords | 非貴金属錯体 / メタノール / 脱水素化 / 光反応 / ホルムアルデヒド / 水素ラジカル / アミノフェノール / レドックス活性配位子 / 錯体 / 光脱水素化 / MeOH / 光脱水素 / 非貴金属触媒 / 室温駆動 / 水素発生量子収率 |
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| Outline of Final Research Achievements |
Dehydrogenation of anhydrous methanol is of great importance, given its ubiquity as an intermediate for the production of a large number of industrial chemicals. Since dehydrogenation of methanol is an endothermic reaction, heterogeneous or homogeneous precious-metal-based catalysts and high temperatures are usually required for this reaction to proceed. Here we report the photochemical dehydrogenation of anhydrous methanol at room temperature catalysed by o-aminophenol (apH2), o-aminophenolate (apH－) and the non-precious metal complex trans-[FeII(apH)2(MeOH)2]. Under excitation at 289 nm and in the absence of additional photosensitizers, these photocatalysts generate hydrogen and formaldehyde from anhydrous methanol with external quantum yields of 2.9%, 3.7% and 4.8%, respectively, which are the highest values reported so far to the best of our knowledge. Mechanistic investigations reveal that the photo-induced formation of hydrogen radicals triggers the reaction.
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