共价三嗪骨架纳米多孔聚合物的设计，合成及其性能研究
发布时间：2018-11-06 13:53
【摘要】：碳捕获和存储(CCS)已被确定是一种减少二氧化碳人为排放的有效方法,但这仍然是能源部门面临的最紧迫的挑战。许多新兴材料被开发,典型材料像纳米多孔有机聚合物(CTFs)。有效和可逆的吸附-解吸可能提供一种简单,经济和有效的大量捕获二氧化碳的方法。此外,高比表面积,良好的物理化学稳定性,低骨架密度和大量可用的结构改性方法使CTFs成为CCS工艺的最有希望的候选材料之一。孔隙表面性质决定主体材料和客体气体分子之间固有的相互作用,是确定气体吸附能力和选择性的关键因素之一。主体-客体相互作用同时适合于气体捕获和可逆释放。首先,以三嗪环为基础,为了调节所需的孔径和表面极性,从而改善框架-气体相互作用,通过比较两种经典的修饰策略(前修饰和后修饰),分别用于通过锚定乙酸乙酯基,乙羧基或乙酰肼用于有效的CO2捕获而附加到孔壁上。利用前修饰策略,乙羧基或乙酰肼附加的二氰基咔唑可以构建具有定量的功能官能团的共价三嗪骨架(CTF-CSU36@pre,CTF-CSU37@pre)。而在后修饰情况下,通过咔唑为基础的三嗪骨架与侧基乙酸乙酯基(CTF-CSU20)的水解或酰肼反应以产生具有所需乙羧基(CTF-CSU36@post)或乙酰肼基(CTF-CSU37@post)。通过修饰,其中CTF-CSU37@post具有最高的吸附量(273 K/1 bar为15.9 wt%,273 K/0.15 bar为5.7 wt%),优异的重复使用性和选择性(CO2/N2=115.6)的多孔材料,表明它们具有高效气体存储和分离效率。其次,以三嗪环为基础,选择对氰基苯为基本构筑单元,通过对对氰基苯进行修饰,分别引入一些类似发泡剂的官能团,作为取代基(一个羧基基团、一个羧酸钠基团、两个羧基基团和两个羧酸钠基团),获得一系列1,4-二氰基苯的衍生物,通过氯化锌熔融法聚合后得到拓扑结构类似的一系列CTFs材料(CTF-CSU38、CTF-CSU39、CTF-CSU40和CTF-CSU41)。对于这些聚合物,CTF-CSU38在低压下显示出非常高的CO2吸附能力(273 K/0.15 bar下CO2吸附量为7.9 wt%,273 K/1 bar下CO2吸附量为9.9 wt%)以及良好的IAST选择性(CO2/N2=72.0),并且这种CTFs的选择性甚至优于大多数高比表面积的有机聚合物吸附剂。其中CTF-CSU38具有对SO2的最高的吸附量达到42.88wt%。这种特定的孔表面工程对聚合物的修饰是一个简单而有效的方法。
[Abstract]:Carbon capture and storage (CCS) has been identified as an effective way to reduce anthropogenic emissions of carbon dioxide, but it remains the most pressing challenge for the energy sector. Many new materials have been developed, typical materials such as nano-porous organic polymer (CTFs). Efficient and reversible adsorption-desorption may provide a simple, economical and efficient method for mass capture of carbon dioxide. In addition, high specific surface area, good physical and chemical stability, low skeleton density and a large number of available structural modification methods make CTFs one of the most promising candidate materials for CCS process. The nature of pore surface determines the inherent interaction between host materials and guest gas molecules, which is one of the key factors in determining the adsorption capacity and selectivity of gas. The host-guest interaction is suitable for both gas capture and reversible release. First, based on triazine ring, in order to adjust the required pore size and surface polarity to improve the frame-gas interaction, two classical modification strategies (pre-modification and post-modification) were compared, respectively, by anchoring the ethyl acetate group. Ethyl carboxyl or acetyl hydrazine is used for efficient CO2 capture and attached to the hole wall. By using the premodification strategy, the covalent triazine skeleton (CTF-CSU36@pre,CTF-CSU37@pre) with quantitative functional groups could be constructed by adding dicyanocarbazole to ethylcarboxyl or acetyl hydrazine. After modification, the triazine skeleton was hydrolyzed with ethyl acetate (CTF-CSU20) or hydrazide to produce the desired ethylcarboxyl (CTF-CSU36@post) or acetylhydrazide (CTF-CSU37@post). By modification, CTF-CSU37@post has the highest adsorption capacity (273K / 1 bar = 15.9 wt%,273 K / 0.15 bar = 5.7 wt%), excellent reusability and selectivity (CO2/N2=115.6). It shows that they have high efficiency in gas storage and separation. Secondly, based on triazine ring, p-cyanobenzene was selected as the basic building unit. By modifying p-cyanobenzene, some functional groups similar to foaming agent were introduced as substituents (one carboxyl group, one carboxylate sodium group). Two carboxyl groups and two sodium carboxylate groups were used to obtain a series of derivatives of 1h4- dicyanobenzene. A series of CTFs materials (CTF-CSU38,CTF-CSU39,CTF-CSU40 and CTF-CSU41) with similar topological structure were obtained by zinc chloride melt polymerization. For these polymers, CTF-CSU38 showed a very high CO2 adsorption capacity at low pressure (CO2 adsorption capacity was 7.9 wt%, at 273K / 0.15 bar). The adsorption capacity of CO2 at 273K / 1 bar is 9.9 wt%) and the IAST selectivity (CO2/N2=72.0) is good, and the selectivity of this CTFs is even better than that of most organic polymers with high specific surface area. The highest adsorption capacity of CTF-CSU38 to SO2 is 42.88 wt. This particular pore surface engineering is a simple and effective method for polymer modification.
【学位授予单位】：石河子大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631.3
本文编号：2314470
[Abstract]:Carbon capture and storage (CCS) has been identified as an effective way to reduce anthropogenic emissions of carbon dioxide, but it remains the most pressing challenge for the energy sector. Many new materials have been developed, typical materials such as nano-porous organic polymer (CTFs). Efficient and reversible adsorption-desorption may provide a simple, economical and efficient method for mass capture of carbon dioxide. In addition, high specific surface area, good physical and chemical stability, low skeleton density and a large number of available structural modification methods make CTFs one of the most promising candidate materials for CCS process. The nature of pore surface determines the inherent interaction between host materials and guest gas molecules, which is one of the key factors in determining the adsorption capacity and selectivity of gas. The host-guest interaction is suitable for both gas capture and reversible release. First, based on triazine ring, in order to adjust the required pore size and surface polarity to improve the frame-gas interaction, two classical modification strategies (pre-modification and post-modification) were compared, respectively, by anchoring the ethyl acetate group. Ethyl carboxyl or acetyl hydrazine is used for efficient CO2 capture and attached to the hole wall. By using the premodification strategy, the covalent triazine skeleton (CTF-CSU36@pre,CTF-CSU37@pre) with quantitative functional groups could be constructed by adding dicyanocarbazole to ethylcarboxyl or acetyl hydrazine. After modification, the triazine skeleton was hydrolyzed with ethyl acetate (CTF-CSU20) or hydrazide to produce the desired ethylcarboxyl (CTF-CSU36@post) or acetylhydrazide (CTF-CSU37@post). By modification, CTF-CSU37@post has the highest adsorption capacity (273K / 1 bar = 15.9 wt%,273 K / 0.15 bar = 5.7 wt%), excellent reusability and selectivity (CO2/N2=115.6). It shows that they have high efficiency in gas storage and separation. Secondly, based on triazine ring, p-cyanobenzene was selected as the basic building unit. By modifying p-cyanobenzene, some functional groups similar to foaming agent were introduced as substituents (one carboxyl group, one carboxylate sodium group). Two carboxyl groups and two sodium carboxylate groups were used to obtain a series of derivatives of 1h4- dicyanobenzene. A series of CTFs materials (CTF-CSU38,CTF-CSU39,CTF-CSU40 and CTF-CSU41) with similar topological structure were obtained by zinc chloride melt polymerization. For these polymers, CTF-CSU38 showed a very high CO2 adsorption capacity at low pressure (CO2 adsorption capacity was 7.9 wt%, at 273K / 0.15 bar). The adsorption capacity of CO2 at 273K / 1 bar is 9.9 wt%) and the IAST selectivity (CO2/N2=72.0) is good, and the selectivity of this CTFs is even better than that of most organic polymers with high specific surface area. The highest adsorption capacity of CTF-CSU38 to SO2 is 42.88 wt. This particular pore surface engineering is a simple and effective method for polymer modification.
【学位授予单位】：石河子大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631.3
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