2023 Fiscal Year Research-status Report
Development of mixed oxide catalyst for carbon dioxide hydrogenation to methanol.
| Project/Area Number |
22K04821
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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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| Keywords | Carbon Dioxde / Hydrogenation / methanol |
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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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| Causes of Carryover |
As per the original proposal, I plan to present the results of this research in the International Congress of Catalysis schedule to be organized in France in July 2024. Owing to the recent weakening of Japanese Yen, the cost of travel will be significantly higher than expected. Therefore a part of fund from FY2023 will be used in FY2024 for this purpose.
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| Remarks |
Abhijit Shrotri received the Encouragement Award from catalysis society of Japan for work related to this project.
2022年度触媒学会奨励賞, 二酸化炭素およびバイオマス資源活用のための触媒開発, 一般社団法人触媒学会, 2023年3月16日.
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