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결정성 다공성 물질의 응용: 선택적인 거울상 이성질체의 흡착과 리튬 이온 배터리의 고체 전해질 물질, 슈퍼 캐퍼시터의 전극 물질

결정성 다공성 물질의 응용: 선택적인 거울상 이성질체의 흡착과 리튬 이온 배터리의 고체 전해질 물질, 슈퍼 캐퍼시터의 전극 물질
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This thesis describes the synthesis, structures and applications of metal-organic frameworks (MOFs) and organic porous materials. A homochiral MOF for enantioselective sorption of racemic alcohols, organic molecular porous materials toward solid electrolyte of lithium-ion battery, and hierarchical porous carbon materials prepared by direct carbonization of MOFs, which may be useful as electrode materials for supercapacitor, are presented. In view of a growing demand for chiral pure compounds in various chemical processes, the homochiral metal-organic framework has become significant because of their potential applications in chiral separation. In chapter 2, enantioselective sorption of racemic alcohols using zinc(II) lactate-terephthalate [Zn2bdc(L-lac)(dmf)], where bdc = terephthalate, L-lac = L-lactate, and dmf = dimethylformamide, is described. This framework contains L-lactic acid as a chiral component. Moderate enantioselective sorption between the host and guest molecules was demonstrated by HPLC (high performance liquid chromatography) and optical rotation method. The difference in interactions between the host and guest molecules was demonstrated by DSC (differential scanning calorimetry). Furthermore, single crystal X-ray diffraction study provided a comprehensive understanding of the nature of the host-guest interactions and chiral recognition. In chapter 3, the synthesis of solid electrolytes for lithium-ion battery using an organic molecular porous material and porous cucurbit[6]uril (PCB[6]), and their Li-ion conductivities are described. The PCB[6]-based solid electrolyte material was prepared by evacuation of guest molecules inside the channels of PCB[6], which was prepared by recrystallization of CB[6] from a dilute aqueous HCl solution. To the guest-free PCB[6] was added lithium salts such as LiClO4 and LiPF6 dissolved in carbonate electrolyte. The lithium-ion conductivities are 9.1 x 10-5 S•cm-1 for PCB[6]•0.8LiPF6•3PC and 2.1 x 10-5 S•cm-1 for PCB[6]•0.4LiClO4•3.4PC, which are 3 orders of magnitude higher than that of guest-free PCB[6] itself. In chapter 4, the preparation of hierarchical porous carbon materials and their application as electrode materials for supercapacitor are described. Four hierarchical porous carbon materials (PCs) were prepared by direct carbonization of MOFs such as MOF-5, Zn2(bdc)2(dabco), Zn2(bdc)(L-lac), and Zn3(fumarate)3(dmf)2. Brunauer–Emmett– Teller (BET) surface areas of the four PCs were in the range of 1000 - 1820 m2/g. Pore size analysis data showed the PCs had hierarchical pores including micro-, meso-, and macropores with a wide pore size distribution. The performance of the PCs as electrode materials for supercapacitor was tested. They showed high capacitance with a capacitance range between 164 - 203 F g-1 at a scan rate of 10 mV s-1. While the capacitance of the four PCs was not correlated with their surface areas, the PCs with ~1% nitrogen contents, PC-2, and PC-4 showed much higher capacitance than the others. This result suggests that nitrogen may act as a doping element in the PCs, which results in the enhancement of the electric property of PCs. Direct carbonization of nitrogen containing MOFs may thus be a promising way for the preparation of porous carbon electrode for supercapacitors.
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