2022 Fiscal Year Annual Research Report
| Project/Area Number |
22J11458
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| Allocation Type | Single-year Grants |
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| Research Institution | University of Toyama |
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Principal Investigator |
姚 杰 富山大学, 工学部, 特別研究員(PD)
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| Project Period (FY) |
2022-04-22 – 2024-03-31
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| Keywords | Carbonylation / Zeolite / Spatial Assembly / Copper |
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| Outline of Annual Research Achievements |
Metal copper was certified as the best promoter in carbonylation of dimethyl ether (DME) to methyl acetate (MA) over mordenite (MOR) zeolite. To date, the major reaction mechanism suggested that the activation of either CO or DME needed assistance from both metal functional sites and Bronsted acid sites (BAS) in zeolites. Therefore, almost all reported Cu modified MOR catalysts employed the preparation method of impregnation or ion exchange for a closer connection. However, the impact of intimacy between copper and BAS at different scales is still not well described.
In the past year, we designed and prepared catalysts with different spatial assembly styles. Cu/MOR and Cu-MOR with the distance between Cu and BAS of zeolite in nanoscale were prepared by impregnation and ion exchange respectively. The Cu/SiO2&H-MOR was prepared via mixing, grinding, and pelleting of Cu/SiO2 with MOR. For Cu/SiO2+H-MOR style, Cu/SiO2 particles and pelleted H-MOR granules were mixed without further grinding. The Cu/SiO2//H-MOR and H-MOR//Cu/SiO2 represent the completely separated assembly style (centimeter-scale). The STY of MA over Cu/SiO2&H-MOR was found to increase from 1725 to 2946 mmol/(kg h) along with raising the reduced temperature.
However, here we adopted the mixture catalyst of Cu/SiO2 and H-MOR, in which the distance between the metal and BAS was much farther than the conventional Cu/MOR and Cu-MOR catalysts by former researchers. Therefore, the intrinsic mechanism of DME carbonylation in our catalytic system should be fundamentally different from all of the previous reports.
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| Current Status of Research Progress |
Current Status of Research Progress
1: Research has progressed more than it was originally planned.
Reason
In the past year, we prepared a series of catalysts with different organizations of active sites, set up the reactors, and completed the activity evaluation. Utilizing a reverse strategy of catalytic reaction design, we separated the partner catalyst from its mother catalyst on a centimeter scale, which allowed the reconstruction of a completely new reaction network with greatly improved catalytic performance compared to the previous catalytic performance.
The progress made in the past year is beyond expectations.
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| Strategy for Future Research Activity |
To get deep insights into the found interesting phenomenon, the in-situ DRIFTS will be conducted to reveal the reactant's activation mechanism that occurred on the single Cu/SiO2 catalyst. According to the result of characterization, the activated DME and CO on Cu/SiO2 should quickly form a key species molecule. This molecule should be a key intermediate in the following DME carbonylation reaction over the H-MOR catalyst. And other characterizations will also be underway to provide additional support for this finding.
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