DC Field | Value | Language |
---|---|---|
dc.contributor.advisor | Lee, Yunho | - |
dc.contributor.advisor | 이윤호 | - |
dc.contributor.author | Bae, Choongman | - |
dc.contributor.author | 배충만 | - |
dc.date.accessioned | 2017-03-29T02:43:24Z | - |
dc.date.available | 2017-03-29T02:43:24Z | - |
dc.date.issued | 2016 | - |
dc.identifier.uri | http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=649775&flag=dissertation | en_US |
dc.identifier.uri | http://hdl.handle.net/10203/222061 | - |
dc.description | 학위논문(석사) - 한국과학기술원 : 화학과, 2016.2 ,[iv, 55 p. :] | - |
dc.description.abstract | Carbon dioxide has received much attention as an abundant, nontoxic and renewable C1 source. One of the promising areas is a coupling reaction of $CO_2$ and epoxides to produce industrially important commodity chemicals, polycarbonates and cyclic carbonates. Cyclic carbonates have potential applications in various indus-tries as the intermediate of organic synthesis, solvents of electrolyte and precursors for polycarbonates. In order to work with the effective and selective conversion of $CO_2$ to cyclic carbonate, we have designed a new type of a ligand scaffold that can accommodate a preorganized iron center. Specifically, we are developing a new catalyst based on understanding the relationship between the geometry of a metal center and the catalytic activity. We have synthesized a series of iron and aluminum complexes supported by tri-anionic tetradentate $C_s$ symmetric $NO_3^{3-}$ ligand (1a, $NO_3H_3$ = (E)-2,2'-(((2-hydroxybenzylidene)amino)methylene)diphenol) and its analogue sub-stituted with a nitro group $(5-NO_2)NO_3^{3-}$ (1b, $(5-NO_2)NO_3H_3$= (E)-2,2'-(((2-hydroxy-5-nitrobenzylidene)amino)methylene)diphenol) in order to accommodate pre-organized rigid structure for 6-coordinate species. A series of iron and aluminum complexes, ${(NO_3)Fe(THF)}_2 (Fe-1a), {(5-NO_2)NO_3}Fe}_2 (Fe-1b), {(NO_3)Al}_2 (Al-1a)$ and ${(5-NO_2)NO_3}Al (Al-1b)$ were fully characterized including X-ray crystallog-raphy. Solid state structures revealed the dimeric nature of Fe-1a, Fe-1b and Al-1a where the available binding sites for each metal center are occupied by bridging phenolate oxygen atoms, while Al-1b exhibits mononuclear 5-coordinate environment. The coupling reaction of $CO_2$ with propylene oxide (PO) was investigated using Fe-1a, Fe-1b, Al-1a and Al-1b as a catalyst. Among these complexes, Fe-1a exhibited highest catalytic activity for the selective synthesis of propylene carbonate. In order to achieve the high catalysis with Fe-1a, several varia-bles including pressure, temperature and co-catalyst/catalyst ratio were adjusted. Under the optimized reaction conditions, Fe-1a showed unusual $4,400 (h^{-1})$ TOF values toward propylene oxide. | - |
dc.language | eng | - |
dc.publisher | 한국과학기술원 | - |
dc.subject | carbon dioixde | - |
dc.subject | cyclic carbonate synthesis | - |
dc.subject | dinuclear iron complex | - |
dc.subject | 이산화 탄소 | - |
dc.subject | 고리형 카보네이트 합성 | - |
dc.title | Developing preorganized iron catalyst for the selective coupling reaction of carbon dioxide with epoxide | - |
dc.title.alternative | 선택성 높은 이산화탄소와 에폭사이드 짝지음 반응용 철 촉매 개발 연구 | - |
dc.type | Thesis(Master) | - |
dc.identifier.CNRN | 325007 | - |
dc.description.department | 한국과학기술원 :화학과, | - |
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