In the first part, the mechanisms for the dissociation of TPA are studied under three types of conditions. The unimolecular dissociation is initiated by the breaking of either the N-Calpha and Calpha -Cbeta bonds and leads to many complicated processes. Within the confined space inside neutral zeolite channels, the diffusion of H radicals enhances a cycle of reactions, which accounts for the experimental observation of dipropylamine and monopropylamine. In the presence of an acidic site, the dissociation of TPA goes through catalyzed successive steps to produce ammonia and propylene molecules. / In the last part, two distinct paths are proposed to investigate the carbon nanotube growth mechanism using benzene as the growth seed and propylene as carbon resource. There is an incremental aromatization process, involving both alkylation and dehydrogenation, that leads to linked aromatic rings to form either (3,3) tube or (4,2) tube. Two paths are identified, one via toluene and the other via cumene. The cumene path is more favorable as the barrier is significant lower. / In the second part, A T5 cluster model is used to investigate mechanisms of propylene aromatization to benzene, which involves chemisorption, dimerization, cyclization and dehydrogenation. Propylene can be chemisorbed to form two distinct products, n-propoxide and i-propoxide, which can further be dimerizated to form longer chain olefins 1-hexene and 2-hexene (from n-propoxide), and 4-methyl-1-pentene and 4-methyl-2-penetene (from i-propoxide). Initiated by H2 elimination, these dimerization products can further go through cyclization process to generated either 6-member ring cyclohexene or 5-member ring methyl-cyclopentene. Catalyzed by zeolite, cyclohexene can directly dehydrogenate to form benzene whereas methyl-cyclopentene can dehydrogenate to form fulven, an isomer to benzene. Under acidic zeolite environment, a fulvene can readily be transformed to the thermodynamically more stable benzene. / The growth mechanisms of mono-sized and parallel-aligned single wall carbon nanotube (CNT) in the microporous channels of AlPO4-5 are investigated by density functional theory calculations. Detailed mechanisms are proposed for the decomposition of TPA, the formation of aromatic ring, and the growth of carbon nanotubes. / Liu, Jianwen. / Adviser: Zhifeng Liu. / Source: Dissertation Abstracts International, Volume: 70-09, Section: B, page: . / Thesis submitted in: December 2008. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 98-99). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.
| Identifer | oai:union.ndltd.org:cuhk.edu.hk/oai:cuhk-dr:cuhk_344411 |
| Date | January 2009 |
| Contributors | Liu, Jianwen, Chinese University of Hong Kong Graduate School. Division of Chemistry. |
| Source Sets | The Chinese University of Hong Kong |
| Language | English, Chinese |
| Detected Language | English |
| Type | Text, theses |
| Format | electronic resource, microform, microfiche, 1 online resource (xii, 99 leaves : ill.) |
| Rights | Use of this resource is governed by the terms and conditions of the Creative Commons “Attribution-NonCommercial-NoDerivatives 4.0 International” License (http://creativecommons.org/licenses/by-nc-nd/4.0/) |
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