| Project/Area Number |
22K04821
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Multi-year Fund |
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| Section | 一般 |
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| Review Section |
Basic Section 27030:Catalyst and resource chemical process-related
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| Research Institution | Hokkaido University |
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Principal Investigator |
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| Project Period (FY) |
2022-04-01 – 2025-03-31
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| Project Status |
Granted (Fiscal Year 2023)
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| Budget Amount *help |
¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
Fiscal Year 2024: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2023: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2022: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
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| Keywords | Carbon Dioxde / Hydrogenation / methanol / Carbon dioxide / hydrogenation / mixed oxide catalyst / CO2 hydrogenation / Methanol / Oxide catalyst |
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| Outline of Research at the Start |
Direct hydrogenation of carbon dioxide to methanol is highly attractive to reduce the use of fossil derived fuels and chemicals. However selective synthesis of methanol is challenging due to simultaneous formation of carbon monoxide. This study aims to develop multi component mixed oxide catalysts for methanol synthesis. Catalysts with oxygen vacancies will be synthesized by doping metals into metal oxide supports. Surface properties of mixed oxide will be tuned to favor the methanol formation.
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| Outline of Annual Research Achievements |
The objective of this research is to develop mixed oxide catalysts for direct hydrogenation of carbon dioxide to methanol. We previously reported that doped Co-ZrO2 catalysts were effective for stabilization of formate species and found that inclusion of In to obtain a dual atom In-Co-ZrO2 catalyst enhances methanol selectivity. In the Co-In-ZrO2 catalyst both Co and In were atomically dispersed and in close proximity of each other. Over the Co-In-ZrO2 catalyst high methanol selectivity was maintained even under low hydrogen partial pressure. Kinetic analysis of the reaction in presence of Co-In-ZrO2 showed that the presence of a dual-atom system influences the order of the reaction. Mechanistic analysis showed that the preferential adsorption of CO2 on Co sites reduces the poisoning effect of adsorbed intermediates because the In site is free for H2 dissociation. As a result, methanol selectivity as high as 86% was obtained.
Furthermore, this concept was expanded to other elements. Inclusion of Ga, Zn, also enhance the methanol selectivity and productivity. In these catalysts as well, the role of CO2 adsorption was limited to Co-Zr interface and the Ga and Zn supported H2 dissociation.
These results were summarized and published in JACS Au journal.
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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
As per the research plan the target of FY2023 was to study the incorporation of third element to achieve high methanol selectivity and investigate the stability of the catalyst. These targets have already been achieved. The plan for FY2024 was to examine the role of each element towards the CO2 hydrogenation pathway. The mechanistic understanding of CO2 hydrogenation over the mixed oxide catalyst is already clear and it is understood that the incorporation of dual atoms alleviates the poisoning effect of adsorbed species and increases methanol selectivity. Furthermore, we have also identified additional elements that can be used in this strategy to achieve higher methanol selectivity.
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| Strategy for Future Research Activity |
The next step is to optimize the metal loading of catalyst to achieve methanol yield above the benchmark of doped metal catalysts that have been reported. Furthermore, we also target the synthesis of methanol under H2 lean conditions to maximize the use of green H2 for methanol synthesis.
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