| 研究課題/領域番号 |
22K04821
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| 研究種目 |
基盤研究(C)
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| 配分区分 | 基金 |
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| 応募区分 | 一般 |
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| 審査区分 |
小区分27030:触媒プロセスおよび資源化学プロセス関連
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| 研究機関 | 北海道大学 |
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研究代表者 |
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| 研究期間 (年度) |
2022-04-01 – 2025-03-31
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| 研究課題ステータス |
交付 (2022年度)
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| 配分額 *注記 |
4,030千円 (直接経費: 3,100千円、間接経費: 930千円)
2024年度: 1,040千円 (直接経費: 800千円、間接経費: 240千円)
2023年度: 1,300千円 (直接経費: 1,000千円、間接経費: 300千円)
2022年度: 1,690千円 (直接経費: 1,300千円、間接経費: 390千円)
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| キーワード | Carbon dioxide / hydrogenation / mixed oxide catalyst / methanol / CO2 hydrogenation / Methanol / Oxide catalyst |
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| 研究開始時の研究の概要 |
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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| 研究実績の概要 |
The goal of this research is to develop mixed metal oxide catalyst for hydrogenation of carbon dioxide to methanol. Based on the proposal work we screened doped catalyst for stabilization of formate species and found that Co-ZrO2 binary catalyst shows high affinity for adsorption of CO2 as carbonate and its hydrogenation to adsorbed formate species. The formate species were adsorbed over the Co-Zr interface, however hydrogenation of formate to methanol was not efficient and methanol selectivity was 30 % even at high Co loading. Dual atom catalyst was prepared by doping In and Co in ZrO2 to overcome this issue. Characterization of catalyst revealed that both In and Co were atomically dispersed. Methanol selectivity increased to 65% over In-Co-ZrO2 catalyst along with increase in methanol yield. Mechanistic investigation showed that Co-Zr interfacial site facilitated the stabilization of formate and In was responsible for hydrogen dissociation for hydrogenation of formate to methanol. Methanol formation was accelerated due to the synergy between Co and In sites. Kinetic analysis showed that the order of reaction with respect to hydrogen reduced from 0.9 for binary catalyst to 0.3 for ternary catalyst indicating that hydrogen activation was promoted over the ternary catalyst.
During screening of catalyst, In-TiO2 binary catalyst showed superior activity for reverse water gas shift reaction at low temperature and high pressure. These results were summarized and published in ChemCatChem journal.
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| 現在までの達成度 (区分) |
現在までの達成度 (区分)
1: 当初の計画以上に進展している
理由
As per the research plan the target was to screen binary catalyst for oxygen vacancy formation and confirm stabilization of formate species in 2022. The plan for FY2023 was to incorporate a third component to enhance methanol formation by promoting formate hydrogenation. We have already achieved synthesis of ternary catalyst that shows better methanol selectivity than individual binary catalyst. In addition, a fair understanding of the mechanistic aspect of ternary catalyst has also been achieved which is ahead of proposed schedule for this work.
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| 今後の研究の推進方策 |
As per the plan the next step is to evaluate the long-term stability of In-Co-ZrO2 catalyst. Furthermore, the while the In-Co-ZrO2 ternary catalyst shows higher methanol yield. Further screening of the third component in ternary catalyst is necessary to improve the methanol yield above the benchmark for doped metal catalysts. Finally, Further clarification for the role of dual atoms sites in ternary towards methanol formation will be evaluated by in-situ mechanistic study.
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