新型多孔有机骨架材料的设计、合成及性能研究

发布时间：2018-08-31 15:58

【摘要】：多孔有机骨架材料POFs凭借其高的比表面积、低的骨架密度、高的稳定性和可修饰性等特点,使其在气体储存、分离和荧光传感等领域有着潜在的应用价值。本论文通过选用低成本及功能化的有机单体,设计和合成了一系列新型的多孔有机骨架材料,并开展了其在气体吸附、荧光传感等领域的应用研究。首先选用廉价易得的三聚氯腈CC为原料,分别与含氮单体4,4’-二(9-咔唑)联苯(CBP)和1,4-双(二苯胺基)苯(DPP)在无水三氯化铝催化剂条件下进行傅氏反应合成了两个三嗪基骨架材料CC-CBP和CC-DPP。CC-CBP和CC-DPP在气体吸附方面有潜在应用,BET比表面积分别为729.5 m~2/g和833.0 m~2/g。在1bar,273K下对CO_2的吸附量分别为115.9 mg/g和150.6 mg/g,对CO_2/N_2的IAST选择性分别为49和75。此外,CC-DPP对H_2展现出较高的的吸附能力(182.4 cm~3/g,1.63 wt%,77 K/1bar)。CC-CBP骨架中具有大的π-共轭体系和大量良好发光性能的咔唑基团,对硝基芳烃类爆炸物TNP和Fe~(2+)具有良好的荧光传感性能,猝灭常数Ksv[TNP]和Ksv[Fe~(2+)]高达18495 M~(-1)和23034.8M~(-1)。其次采用易制备的小分子二苯乙炔DPA和四苯乙烯TPE为单体,分别进行Scholling反应和FDA外交联剂超交联制备多孔聚合物S-DPA、S-TPE和F-TPE,其具有高的BET比表面积和良好的热稳定性。对其进行吸附实验,发现S-DPA、S-TPE和F-TPE在CO_2的捕获和H_2储存方面有良好的应用前景。BET比表面积高达898.0m~2/g(S-DPA)、1208.7 m~2/g(S-TPE)和1270.3 m~2/g(F-TPE)。其中S-TPE在1bar、273K下对CO_2的吸附量高达167.2 mg/g(3.8 mmol/g),在1bar、77K下对H_2的吸附量高达175.2 cm~3/g(1.56 wt%),这归因于其高的微孔体积(0.30 cm~3/g)。荧光测试表明F-TPE具有很好的发光性能,因此我们研究了F-TPE对硝基芳烃爆炸物TNP的荧光传感性能,其Ksv[TNP]数值12192 M~(-1)。最后我们利用3,4,9,10-傒四羧酸酐PTCDA和1,3,5-三(4-氨基苯基)苯TAPB单体在路易斯酸Zn(OAc)_2催化剂、咪唑溶剂中合成两种新型聚酰亚胺材料PI-a和PI-b(有DMSO溶剂)。其中PI-a可以很好的识别Ag~+(turn-off型)和硝基芳烃爆炸物TNP(turn-on型),Ksv[Ag~+]为21916.4 M~(-1),检测限为8.1×10~(-6)mol/L。PI-a在高温下形成碳材料PI-C-600,PI-C-600具有较高的BET比表面积(981.7 m~2/g),同时对CO_2具有很好的吸附能力(129.4 mg/g,273K/1bar)和吸附选择性(CO_2/N_2:68,IAST)。这些结果表明具有傒芳香环和三苯基苯环的聚酰亚胺材料PIs的碳材料在CO_2捕获方面存在很大的发展潜力。
[Abstract]:Because of its high specific surface area, low skeleton density, high stability and modifiability, porous organic skeleton material POFs has potential applications in gas storage, separation and fluorescence sensing. In this paper, a series of new porous organic skeleton materials were designed and synthesized by using low cost and functionalized organic monomers, and their applications in gas adsorption and fluorescence sensing were studied. First, the cheap and easily available CC was used as the raw material. Two triazin-based skeleton materials CC-CBP, CC-DPP.CC-CBP and CC-DPP were synthesized by Fourier reaction with nitrogen-containing monomers 4C4C4- bis (9- carbazole) biphenyl (CBP) and 1- 4- bis (diphenylamino) benzene (DPP) under anhydrous aluminum chloride catalyst, respectively. Two triazine matrix materials, CC-CBP and CC-DPP, were adsorbed in gas. The specific surface area of BET is 729.5 mm2 / g and 833.0 mm2 / g respectively. The IAST selectivity of CO_2 to CO_2/N_2 was 49 and 75 at 1 ~ 273K and 150.6 mg/g, respectively, at 115.9 mg/g and 150.6 mg/g, respectively. In addition, CC-DPP exhibited high adsorption capacity (182.4 cm~3/g,1.63 wt%,77 K/1bar). CC-CBP skeleton had large 蟺 -conjugated system and a large number of carbazole groups with good luminescence. TNP and Fe~ (2) of p-nitroaromatic explosives had good fluorescence sensing properties. The quenching constants Ksv [TNP] and Ksv [Fe~ (2)] are as high as 18495 M-1 and 23034.8 M-1. Secondly, the porous polymers S-DPA-S-TPE and F-TPEwere prepared by Scholling reaction and hypercrosslinking of FDA, using diphenylacetylene DPA and tetrastyrene TPE as monomers, which had high BET specific surface area and good thermal stability. The adsorption experiments show that S-DPA-S-TPE and F-TPE have good application prospects in CO_2 capture and Hap2 storage. The specific surface area of BET is as high as 898.0m~2/g (S-DPA) 1208.7 mg / g (S-TPE) and 1270.3 mt2 / g (F-TPE). The amount of CO_2 adsorbed by S-TPE was up to 167.2 mg/g (3. 8 mmol/g) at 273K and 175.2 cm~3/g (1. 56 wt%) at 1 mg/g 77K, which was attributed to its high micropore volume (0. 30 cm~3/g). The fluorescence measurement shows that F-TPE has good luminescence performance. Therefore, we have studied the fluorescence sensing performance of F-TPE p-nitroaromatics explosive TNP, whose Ksv [TNP] value is 12192 M-1. Finally, two new polyimide materials, PI-a and PI-b (with DMSO solvent), were synthesized by using the monomers of PTCDA and TAPB in Zn (OAc) _ 2 catalyst. PI-a can identify Ag~ (turn-off type) and nitroaromatic explosive TNP (turn-on type) Ksv [Ag~] is 21916.4 M-1, the detection limit is 8.1 脳 10 ~ (-6) mol/L.PI-a at high temperature to form a carbon material PI-C-600,PI-C-600 has a high BET surface area (981.7 mt2g / g), at the same time has a good adsorption ability to CO_2 (129.4). Mg/g,273K/1bar) and adsorption selectivity (CO_2/N_2:68,IAST). These results indicate that the carbon materials of polyimide material PIs with aromatic ring and triphenyl benzene ring have great potential in CO_2 capture.
【学位授予单位】：山西师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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