Synthesis of microporous polymer networks and Control of their electronic structure = 마이크로포러스 폴리머 네트워크의 합성 및 전자구조 제어에 관한 연구

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In this study, new microporous nanostructures so called “Acetylene mediated Conjugated Microporous Polymers (ACMPs)” have been synthesized using acetylene gas as a building unit with functional linkers via the coupling reaction, where the acetylene gas was used as a source of the functional building unit for the first time. Three types of ACMPs have been synthesized in this work. ACMP-C was fabricated by linking Tetrakis(4-iodophenyl)methane with an acetylene gas, whereas ACMP-C6 and ACMP-N were synthesized from 1,3,5-Tris(4-iodophenyl)benzene and Tris(4-iodophenyl)amine, respectively. ACMP-C is giving the highest BET surface area attributed to the tetrahedrally oriented iodine terminals suitable for formation of microporous networks. Meanwhile, ACMP-C6 was synthesized using a planar-type starting building unit with three iodine terminals less suitable for a formation of 3 dimensional networks. The starting building unit of ACMP-N is on the incomplete tetrahedron-type unit along with one lone pair electron, thus leading to a sparse network structure. Also, the structures with the triple-bond linkages have been confirmed by the solid-state 13C CPMAS NMR, consistent with those obtained from FT-IR measurements. In addition, it was identified that the significant CO2 uptake capacity of ACMP-N at 195 K are available due to the micropore network accessible by CO2 with the small kinetic diameter, although the micropore network for ACMP-N was very difficult to be accessed by the N2 molecules with the relatively large kinetic diameter. Meanwhile, as the temperature increases, we found that ACMP-C shows the highest CO2 adsorption capacity among ACMPs with 68.8 mg/g at 273 K and 47.5 mg/g at 298 K. This demonstrates that the increased kinetic diameter of CO2 at high temperatures prevents penetrating into the pores of ACMP-N, although it has lone pair electrons on nitrogen atom for a good interaction site with CO2. ACMP-C shows the smaller CO2 capacity by 3 times than 1,4...
Advisors
Kang, Jeung-Kuresearcher강정구
Description
한국과학기술원 : 신소재공학과,
Publisher
한국과학기술원
Issue Date
2012
Identifier
511845/325007  / 020087093
Language
eng
Description

학위논문(박사) - 한국과학기술원 : 신소재공학과, 2012.8, [ ix, 102p. ]

Keywords

Microporous materials; polymer networks; carbon dioxide storage; hydrogen storage; 마이크로포러스 물질; 폴리머 네트워크; 이산화탄소 저장; 수소 저장; 제일원리 계산; first-principles calculation

URI
http://hdl.handle.net/10203/181975
Link
http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=511845&flag=dissertation
Appears in Collection
MS-Theses_Ph.D.(박사논문)
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