photocatalytic dehydrogenation of methanol by nonprecious-metal-complex bearing redox-active aminochalcogenolato

2016 Fiscal Year Final Research Report

• Project/Area Number: 15K17834
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Inorganic chemistry
• Research Institution: Chuo University
• Principal Investigator: matsumoto takeshi 中央大学, 理工学部, 助教 (40564109)
• Project Period (FY): 2015-04-01 – 2017-03-31
• 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

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.

Free Research Field

化学