| 研究課題/領域番号 |
23KF0237
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| 研究種目 |
特別研究員奨励費
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| 配分区分 | 基金 |
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| 応募区分 | 外国 |
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| 審査区分 |
小区分34010:無機・錯体化学関連
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| 研究機関 | 京都大学 |
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研究代表者 |
堀毛 悟史 京都大学, 理学研究科, 教授 (70552652)
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| 研究分担者 |
WANG SHAOMIN 京都大学, 理学研究科, 外国人特別研究員
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| 研究期間 (年度) |
2023-11-15 – 2026-03-31
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| 研究課題ステータス |
交付 (2023年度)
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| 配分額 *注記 |
2,000千円 (直接経費: 2,000千円)
2025年度: 300千円 (直接経費: 300千円)
2024年度: 1,000千円 (直接経費: 1,000千円)
2023年度: 700千円 (直接経費: 700千円)
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| キーワード | Metal-organic framework / Glass / Membrane / Gas separation |
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| 研究開始時の研究の概要 |
金属イオンと架橋性配位子から組み上がるガラスが新たな非晶質材料として注目されている。本研究では配位高分子ガラスが膜状態で示すガス分子の選択的な溶解現象を利用、制御し、ガス分離特性の獲得を目的とする。膜分離で常にトレードオフとなる「分子選択性」と「透過速度」の両立を実現するため、金属と架橋性配位子が形成するガラスネットワークを制御し、様々なガス分子のサイズや化学的特性を認識する場を構築する。対象とするガスは水素・二酸化炭素・窒素・メタンを念頭とし、高性能膜が得られた暁には、従来の膜技術では難しいオレフィン・パラフィンガス分離機能の発現に取り組む。
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| 研究実績の概要 |
In this study, I propose strategies for the preparation of grain boundary free membranes based on one-dimensional (1D) coordination polymer (CP) glasses with unsaturated metal sites for the separation of olefins and paraffins. During the research period, a series of coordination polymers (CPs) were synthesized and characterized, with special emphasis on variations of the copper-imidazole framework. The 1D CP materials synthesized included Cu(imidazole), Cu(2-isopropylimidazolate), and Cu(2-ethylimidazolate). Each compound was extensively analyzed to determine its fundamental properties. Phase purity was confirmed by powder X-ray diffraction (PXRD), while thermogravimetric analysis (TGA) provided significant insight into the decomposition patterns of the synthesized coordination polymers (CPs). In addition, differential scanning calorimetry (DSC) was used to investigate the thermal behavior and melting points of the materials. This characterization provides a solid basis for future application-oriented research on these CPs. In the next phase of the research, different methods for fabricating membranes from coordination polymer (CP) glasses were explored. CP powders were directly heated to form membranes, and a hot-slipping technique with an alumina (Al2O3) substrate was used after melting the CPs. The goal was to develop effective processes to produce uniform and functional CP membranes suitable for potential applications.
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| 現在までの達成度 (区分) |
現在までの達成度 (区分)
2: おおむね順調に進展している
理由
The research used a combination of two one-dimensional coordination polymer (CP) materials, Cu(2-isopropylimidazolate) and Cu(2-ethylimidazolate), to create membrane materials. The gas diffusion capabilities of the membranes were evaluated using a membrane separation system. The membranes were prepared by heating a powder mixture of the two CPs, resulting in thick membranes. The gas permeability of CO2; and N2; through the membranes was evaluated at various temperatures ranging from 25 to 200 °C. An oven was used to precisely control the test temperatures, while Ar gas was used as a carrier and purge gas for chromatography. This setup provided a stable and controlled environment, which was essential for accurate assessment of gas permeability in the membranes. The experimental results clearly show that the permeability of CO2 increases with temperature, reaching 16 GPU at 200°C. This highlights the remarkable gas permeability of one-dimensional non-porous CP glass materials, despite the relatively low gas permeance. To reduce the thickness of the membrane, 30 mg of the P0.5E0.5 mixture was heated and hot-slipped onto an Al2O3 substrate. This resulted in a thinner membrane that retained its functional properties.
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| 今後の研究の推進方策 |
A variety of techniques will be used to control parameters such as membrane thickness and uniformity in order to optimize the amount of material used to fabricate the membranes. In the future, an investigation of the manufacturing processes of coordination polymer (CP) membrane materials will be conducted. A variety of techniques will be used to control parameters such as membrane thickness and uniformity in order to optimize the amount of materials used in the production of membranes. To improve the precision and quality of membrane production, it may be necessary to utilize tools such as doctor blades and spin coaters. In addition, the range of gases tested will be expanded to include hydrogen, methane, ethane and ethylene to investigate the separation performance of the CP membranes against these gases. In addition, the separation performance of the membranes will be evaluated at temperatures both above and below the glass transition temperature (Tg) to determine the optimal temperature for membrane separation. The interaction mechanisms of gas molecules with membrane materials will be elucidated using various characterization techniques. Theoretical calculations and other methods will be used to further investigate these interactions.
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