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咔唑基共轭微孔聚合物的合成与应用研究
黄伟
Thesis Advisor阳仁强
2015-05
Degree Grantor中国科学院大学
Place of Conferral北京
Degree Discipline材料工程
Keyword共轭微孔聚合物 咔唑 气体吸附 能源存储
Abstract共轭微孔聚合物是一类新型有机多孔材料,其具有比表面积大、物理化学稳定性高、共轭体系等优点。与无机材料相比较,共轭微孔聚合物可以通过化学修饰或分子设计等方法来实现对材料结构和性能的改变,从而获得具有不同性质的材料,该类材料可广泛应用于气体的选择性吸附等方面。通过结构设计,也可以得到有机无机掺杂的复合材料,使材料兼具二者的优点,扩展材料在环境领域的应用。独特的共轭电子体系兼具多孔性质使共轭微孔聚合物又可以应用于锂/钠离子电池,从而存储能源。 咔唑基团具有独特的刚性结构,且容易进行氧化聚合,是目前报道的较好的用于合成共轭微孔聚合物的基础单元,因此本论文采用咔唑基团为主要研究对象,设计合成了一系列咔唑基共轭微孔聚合物,并通过核磁、红外光谱等手段表征聚合物分子水平结构,通过N2、CO2、H2、CH4气体在不同温度下的吸附等温线研究咔唑基聚合物材料孔径结构和气体存储能力间的关系;通过将其应用于锂离子电池和钠离子电池中,研究材料电化学储锂/钠性能及其机制。论文主要包括以下内容: 第一章:共轭微孔聚合物文献综述。 第二章:以乙烯咔唑为单体,采用自由基聚合和氧化聚合两种方法,以不同顺序的聚合顺序进行合成,得到四种共轭微孔聚合物。性能研究表明,在相同单体下,不同的聚合方法和合成路线,都会对材料的结构性能产生较大的影响。 第三章,延续第二章的研究,采用较优的合成路线,制备了具有新型核-空腔-壳结构的掺杂磁性的共轭微孔聚合物,该系列材料具有多级孔径结构和大的孔容,可应用于水体有机污染物及海上溢油污染消除等方面。 第四章,以苯并噻二唑为中心,咔唑为刚性聚合基团,设计合成共轭微孔聚合物。由于合成的微孔聚合物具有多个氧化还原位点,大的比表面积和适宜的孔径,该聚合物展现了优异的电化学储锂/钠性能,是一种非常有前景的清洁可持续能源存储材料。 第五章,本论文总结。
Other AbstractConjugated microporous polymers (CMPs) are a new series of organic porous materials with large surface areas, high physical and chemical stability, and π-conjugated system in the structure. Compared with inorganic porous materials, CMPs can be easily chemically modified or structurally designed to change the rigid backbone of the materials and thus obtain optimal performance in gas storage. By the structure designing, hybrid (organic and inorganic) materials can be prepared, which could have the advantages of both materials. These materials can be employed in environmental field. The unique conjugated systems prompt the polymers in application of Li/Na battery for energy storage. Design and synthesis of carbazole-based conjugated microporous polymers and characterizing them by NMR, IR spetra, gas (N2, CO2, H2, CH4) uptake and battery efficiency tests are the main works in this thesis. The thesis mainly includes the following parts: Part I: a general over view of the conjugated microporous polymers. Part II: four (N-vinyl carbazole)-based polymers were prepared through two facile synthetic strategies including both free radical polymerization and oxidative polymerization in different sequences. The results show that the sequence and polymerization method can make a great difference on the performance of materials even using the same monomer. Part III: multifunction hybrid materials were prepared with novel Fe3O4@spacer@CMPs (core-spacer-shell) structure. Magnetism, conjugated system, large pore volume and ultramicroporous structure are combined in one bulk materials. These materials can be tools for pollutants recycling, electromagnetism, photoelectricity and biological medicine. Part IV: a micropurous conjugated polymer was synthesized with [2,1,3]-benzothiadiazole as core and carbazole as rigid group. It can be used as high-performance electrode materials for lithium and sodium storage attributing to their conductive frameworks, plentiful redox-active units, high specific surface area and homogeneous microporous structure. The polymers showed excellent electrochemical performance lithium storage/sodium, is a very promising clean and sustainable energy storage materials Part V: the conclusion of the thesis.
Department先进有机功能材料团队
Date Available2015-07
Subtype硕士 ; 学位论文
Language中文
Document Type学位论文
Identifierhttp://ir.qibebt.ac.cn/handle/337004/8097
Collection先进有机功能材料团队
Affiliation中国科学院青岛生物能源与过程研究所
Recommended Citation
GB/T 7714
黄伟. 咔唑基共轭微孔聚合物的合成与应用研究[D]. 北京. 中国科学院大学,2015.
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