| Project/Area Number |
16074209
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
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| Research Institution | Kyoto University |
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Principal Investigator |
KITAGAWA Susumu Kyoto University, Institute for Integrated Cell-Material Sciences, Deputy Director (20140303)
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| Co-Investigator(Kenkyū-buntansha) |
OHBA Masaaki Kyoto University, Graduate school of Engineering, Associate Professor (00284480)
CHANG Ho-Chol Kyoto University, Graduate school of Engineering, Assistant Professor (60335198)
UEMURA Takashi Kyoto University, Graduate School of Engineering, Assistant Professor (50346079)
INAGAKI Shinji Kyoto University, Toyota Central R&D Labs., Inc., Group Leader (30374086)
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| Project Period (FY) |
2004 – 2007
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| Project Status |
Completed (Fiscal Year 2007)
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| Budget Amount *help |
¥127,000,000 (Direct Cost: ¥127,000,000)
Fiscal Year 2007: ¥22,200,000 (Direct Cost: ¥22,200,000)
Fiscal Year 2006: ¥22,200,000 (Direct Cost: ¥22,200,000)
Fiscal Year 2005: ¥75,500,000 (Direct Cost: ¥75,500,000)
Fiscal Year 2004: ¥7,100,000 (Direct Cost: ¥7,100,000)
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| Keywords | Porous metal complexes / multi-functions / polymer synthesis / mesoporous silica / ナノ空間 / 金属錯体 / ガス吸着 / 反応場 / 物性 / 多孔性多孔性配位高分子 / 分子配列 / 磁性誘電癒合 / 触媒能 / 入子構造 / 直接観測 / 動的骨格 / アセチレン / 分離 / 吸着 / 水素吸蔵 |
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| Research Abstract |
In this project, we aim to develop functions with the characteristics of porous coordination polymers (PCPs)such as designable surface functionality, high regularity, and framework flexibility Highly controlled acetylene accommodation in a microporous coordination polymer has been accomplished by preparing a pore surface specific for acetylenic hydrogen atoms. The acetylene can be packed 200 times as densely as the limitation value without explosion. The adsorbed acetylene molecules are highly stabilized by the double hydrogen bonded supports in nanosized pores, which mere revealed by direct observation of the adsorbed molecules using the results of in-situ synchrotron XRD measurements and by first principles calculations.
We have designed and synthesized a bimodal microporous twofold interpenetrating PCP with two types of channel for anionic N(CN)2- and neutral water molecules, respectively. The dehydrated framework provides a dual function of specific anion exchange of free N(CN)2- for the smaller N3- anions and selective gas sorption. The N3--exchanged framework leads to a dislocation of the mutual positions of the two interpenetrating frameworks, resulting in an increase in the effective pore size in one of the counterparts of the channels and a higher accommodation of adsorbate than in the as-synthesized framework.
A few substituted acetylenes spontaneously polymerized in one-dimensional nanochannels of PCPs with pillared layer structure. In this polymerization system, only mono-substituted acetylenes with electron-withdrawing group could be polymerized in the channels. suggesting that strong hydrogen bonding interaction between the monomers and surface carboxylate moiety in the frameworks is a key factor to initiate the polymerization.
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