2019 Fiscal Year Final Research Report

Photochemical dehydration of methanol by single-site-catalyst derived from redox-active metal complex

Research Project

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Project/Area Number	18K19101
Research Category	Grant-in-Aid for Challenging Research (Exploratory)
Allocation Type	Multi-year Fund
Review Section	Medium-sized Section 34:Inorganic/coordination chemistry, analytical chemistry, and related fields
Research Institution	Chuo University
Principal Investigator	Chand Ho-Chol 中央大学, 理工学部, 教授 (60335198)
Co-Investigator(Kenkyū-buntansha)	松本剛東京工業大学, 科学技術創成研究院, 研究員 (40564109) 中田明伸中央大学, 理工学部, 助教 (20845531)
Project Period (FY)	2018-06-29 – 2020-03-31
Keywords	メタノール / 光脱水素 / 錯体触媒 / シングルサイト触媒 / 光反応 / アルミノシリケート / 分子前駆体
Outline of Final Research Achievements	In this work, we quantitatively revealed the relation between photochemical dehydration activity of MeOH via aminophenolato metal complexes and their co-ligands. We found that the complexation of M/apH unit with co-ligand depend on the nature of M and co-ligand. In particular, the activity increases up to 3.9 times when M = Fe with tBuCN as co-ligand with strong sigma-donation ability. These results would contribute towards the construction of single-site dehydration catalysis based on transition metal complexes with ligands with electron/proton pooling properties. In addition to these results, we also succeed in developing new synthesis method of aluminosilicate )zeolite which would be useful as host for molecular catalyst. We found that a molecular cluster with six Si and a Al atom afforded zeolite L and W at around 160 degreeC under hydrothermal condition. It is noteworthy that this processes do not need any pretreatment of precursors which is needed in the conventional methods.
Free Research Field	金属錯体化学
Academic Significance and Societal Importance of the Research Achievements	メタノールの脱水素反応はその学術的意義に加え、POM等の製造において重要である。特に脱水条件化における光脱水素はその独創性に特徴がある。本研究では、我々が見いだしたアミノフェノラート錯体の触媒活性能を向上すべく、分子内因子として、置換基、金属種そして補助配位子の選定を検討した結果、従来の触媒に比べ4倍の触媒能の向上に成功した。その過程にこれらの因子が与える効果について分子レベルで明らかにできたことは今後の触媒設計に有意義な知見で有る。さらに、シングルサイト触媒化を指向し、独自の多孔性担体の合成法の開発に成功したことからも、今後シングルサイト光触媒化の実現に向け重要な知見を得られたと考える。