| 研究課題/領域番号 |
26888005
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| 研究機関 | 東京大学 |
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研究代表者 |
中村 優希 東京大学, 大学院総合文化研究科, 特任助教 (70732676)
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| 研究期間 (年度) |
2014-08-29 – 2016-03-31
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| キーワード | 不均一触媒系 / 多孔質物質 / 触媒活性種 / オレフィンメタセシス / 新規触媒系 |
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| 研究実績の概要 |
The goal of this research is to understand the surface mechanism of the MTO on ZnCl2//meso-Al2O3 catalyst for the metathesis reaction, and apply the obtained knowledge for the development of novel catalytic system. To achieve this goal, the applicant is conducting the mechanistic study in a stepwise manner.
First, MTO catalyst supported by the ZnCl2-modified γ-alumina (γ-Al2O3) will be prepared, and solid-state NMR experiment will be carried out with synthesized 13C-labeled MTO. The catalytic system of γ-Al2O3 will be studied in accordance to the available data of NMR from the mechanistic study reported by Coperet group on the surface structure of MTO on γ-Al2O3 for olefin metathesis reaction. After obtaining the experimental data, the same protocol will be carried out for 13C-labeled MTO on ZnCl2//meso-Al2O3 to explore the reason for high efficiency toward olefin metathesis. Then, the observed information on the active species will be applied to the development of novel heterogeneous catalytic system.
Up to the present point, synthesis of the 13C-labeled MTO has been completed, and the catalytic system of 13C-labeled MTO on γ-Al2O3 was studied via solid-state NMR. By comparing the obtained data to the reference data reported by Coperet, the presence of 13C-labeled MTO on γ-Al2O3 was confirmed. Moreover, the preparation of 13C-labeled MTO on meso-Al2O3 has been also achieved. With the precise protocol in hand, the next step of mechanistic study is ongoing to find the effect of ZnCl2 on the highly efficient active species of the MTO on ZnCl2//meso-Al2O3 catalyst.
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| 現在までの達成度 (区分) |
現在までの達成度 (区分)
3: やや遅れている
理由
The progress of the research has been a bit delayed due to the following two reasons.
The main reason is the preparation of the new chemistry laboratory course for the PEAK (Program in English At Komaba) international students. The work load for organizing this undergraduate chemistry laboratory class includes: translation and edition of the laboratory manual from the Japanese textbook, preparation of the lecture materials provided during the lecture sessions of the course, actual teaching and mentoring of the students, and grading the laboratory reports. Since it was the first time to offer this type of course in English at the University of Tokyo, it took more effort than the applicant has expected to organize the course. However, all of the course materials have been prepared, so the applicant will be able to put more effort on the research in this year.
Another reason for the delay is the challenge in learning and applying the techniques for solid-state NMR and the handling of porous solid catalysts. This is the first time for the applicant to work with the solid catalyst, and the applicant is the only person working on this research project, so it took awhile to get used to the protocols required for investigating mechanistic studies. However, the applicant has managed to overcome this challenge, thus, the progress of the research in this fiscal year is expected to run more smoothly compared to last year.
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| 今後の研究の推進方策 |
With the analytical data obtained from the catalytic system using γ-alumina in hand, mechanistic study of the MTO on ZnCl2//meso-Al2O3 will be carried out. Prepared MTO on ZnCl2//meso-Al2O3 will be analyzed to study their properties as well as to obtain the mechanistic insights of the formation of active species during the olefin metathesis reaction.
Following analyses will be investigated. (1) Composition of catalyst surface: IR, elemental analysis, extended X-ray absorption fine structure (EXAFS), inductively coupled plasma-atomic emission spectroscopy (ICP-AES). (2) Surface properties: N2 adsorption-desorption measurement for (a) surface area via Brunauer-Teller (BET) method and (b) pore-size distribution via Dollimore-Heal (DH) method. (3) Reactive species in the metathesis reaction: single-pulse proton-decoupled 13C magic angle spinning (MAS) solid-state NMR, solid-state 13C cross-polarization (CP) MAS NMR, theoretical calculation.
Obtained mechanistic insights from the mechanistic studies will then be applied for the development of novel catalytic reactions. Understanding the effects of Lewis acid and the advantage of using porous materials with a uniform pore size, these knowledge will be applied to the development of a new catalytic system for several organic reactions, including olefin metathesis. To achieve this goal, combination of the screening of Lewis acid, metal catalyst, as well as reaction medium to develop useful and environmentally friendly catalytic reactions that efficiently proceed under mild condition will be investigated.
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