共價三嗪骨架納米多孔聚合物的設(shè)計，合成及其性能研究
發(fā)布時間：2018-11-06 13:53
【摘要】：碳捕獲和存儲(CCS)已被確定是一種減少二氧化碳人為排放的有效方法,但這仍然是能源部門面臨的最緊迫的挑戰(zhàn)。許多新興材料被開發(fā),典型材料像納米多孔有機聚合物(CTFs)。有效和可逆的吸附-解吸可能提供一種簡單,經(jīng)濟和有效的大量捕獲二氧化碳的方法。此外,高比表面積,良好的物理化學穩(wěn)定性,低骨架密度和大量可用的結(jié)構(gòu)改性方法使CTFs成為CCS工藝的最有希望的候選材料之一。孔隙表面性質(zhì)決定主體材料和客體氣體分子之間固有的相互作用,是確定氣體吸附能力和選擇性的關(guān)鍵因素之一。主體-客體相互作用同時適合于氣體捕獲和可逆釋放。首先,以三嗪環(huán)為基礎(chǔ),為了調(diào)節(jié)所需的孔徑和表面極性,從而改善框架-氣體相互作用,通過比較兩種經(jīng)典的修飾策略(前修飾和后修飾),分別用于通過錨定乙酸乙酯基,乙羧基或乙酰肼用于有效的CO2捕獲而附加到孔壁上。利用前修飾策略,乙羧基或乙酰肼附加的二氰基咔唑可以構(gòu)建具有定量的功能官能團的共價三嗪骨架(CTF-CSU36@pre,CTF-CSU37@pre)。而在后修飾情況下,通過咔唑為基礎(chǔ)的三嗪骨架與側(cè)基乙酸乙酯基(CTF-CSU20)的水解或酰肼反應(yīng)以產(chǎn)生具有所需乙羧基(CTF-CSU36@post)或乙酰肼基(CTF-CSU37@post)。通過修飾,其中CTF-CSU37@post具有最高的吸附量(273 K/1 bar為15.9 wt%,273 K/0.15 bar為5.7 wt%),優(yōu)異的重復(fù)使用性和選擇性(CO2/N2=115.6)的多孔材料,表明它們具有高效氣體存儲和分離效率。其次,以三嗪環(huán)為基礎(chǔ),選擇對氰基苯為基本構(gòu)筑單元,通過對對氰基苯進行修飾,分別引入一些類似發(fā)泡劑的官能團,作為取代基(一個羧基基團、一個羧酸鈉基團、兩個羧基基團和兩個羧酸鈉基團),獲得一系列1,4-二氰基苯的衍生物,通過氯化鋅熔融法聚合后得到拓撲結(jié)構(gòu)類似的一系列CTFs材料(CTF-CSU38、CTF-CSU39、CTF-CSU40和CTF-CSU41)。對于這些聚合物,CTF-CSU38在低壓下顯示出非常高的CO2吸附能力(273 K/0.15 bar下CO2吸附量為7.9 wt%,273 K/1 bar下CO2吸附量為9.9 wt%)以及良好的IAST選擇性(CO2/N2=72.0),并且這種CTFs的選擇性甚至優(yōu)于大多數(shù)高比表面積的有機聚合物吸附劑。其中CTF-CSU38具有對SO2的最高的吸附量達到42.88wt%。這種特定的孔表面工程對聚合物的修飾是一個簡單而有效的方法。
[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.
【學位授予單位】：石河子大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O631.3
本文編號：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.
【學位授予單位】：石河子大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O631.3
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