多孔氢键超分子有机框架材料的制备及其气体吸附分离性能研究

发布时间：2018-03-31 14:28

本文选题：超分子有机框架材料　切入点：慢扩散法　出处：《浙江大学》2017年硕士论文

【摘要】：吸附分离是化工分离过程中一种非常重要的技术,其核心是发展高效的吸附分离材料。金属有机框架材料(Metal organic frameworks,MOFs)和共价有机框架材料(Covalent organic frameworks,COFs)等作为新型多孔材料因具有高比表面积、相对稳定、孔径和性能可调等优点,有用于吸附分离从而替代传统技术的潜能。超分子有机框架材料(Supramolecular organic frame works,SOFs)相较 MOFs和COFs,具有低密度、高柔韧性、易于纯化和再生等优点,却因其较为脆弱的非共价结构网络使得其难以稳定存在而较少用于吸附分离。腺嘌呤与金属离子的有机配合物作为构筑单元,用于制备SOFs材料可同时具备MOFs和SOFs的优点。本文就腺嘌呤类SOFs的设计、合成及其在低碳烃吸附分离中的应用展开讨论,对于发展新型吸附分离材料具有重要的科学研究价值,同时可为轻质烃分离提供了一个新的思路和参考。首先,采用慢扩散合成法合成了多孔氢键超分子有机框架材料MPM-1-Br、MPM-1-Cl和MPM-1-TIFSIX。采用SEM、PXRD、TGA及比表面积分析等技术对材料进行综合表征,并测定了此三种同构多孔氢键超分子有机框架材料对乙炔和二氧化碳单组分气体的吸附等温线。实验结果表明,MPM-1-Br、MPM-1-Cl和 MPM-1-TIFSIX 的比表面积分别为 373 m2·g-1、417 m2·g-1和1020 m2·g-1,且分别在240℃和200℃的温度范围内有良好的稳定性;在298 K和总压100 kPa,通过IAST理论计算得到前两者对50:50 C2H2/CO2混合气体的吸附选择性分别达到了 3.8和3.0,与HKUST-1(4.7)和UTSA-30(3.3)等金属-有机框架材料有相当的分离性能。其次,通过改变离子类型,合成了新型的多孔氢键超分子有机框架材料IPM-SIFSIX-1。采用SXRD、PXRD、光学显微镜、TGA及比表面积分析等技术对材料进行综合表征,并测定了 IPM-SIFSIX-1对多种气体组分的吸附等温线。实验结果表明,IPM-SIFSIX-1的比表面积为339m2·g-1,且具有水热稳定性;在298 K 和总压 100kPa 下对 50:50C2H2/C2H4、50:50C2H2/CO2 和 10:90CO2/N2 混合气体的吸附选择性分别达到了 7.1,4.9和97。其对50:50 C2H2/C2H4的选择性在SOFs中仅次于HOF-1(7.4)。中子衍射实验结果表明IPM-SIFSIX-1a对C2H2/C2H4具有高吸附选择性的性能与C2H2两端能与IPM-SIFSIX-1a结构中的SiF62-形成相对较强的氢键作用有关。而通过将结构崩塌的IPM-SIFSIX-1a浸入水溶液或(NH4)2SiF6水溶液中,我们发现IPM-SIFSIX-1具有自恢复性能。最后,基于IPM-SIFSIX-1具有优越的气体吸附分离性能,通过进一步修饰配体结构,合成了多孔氢键超分子有机框架材料IPM-SIFSIX-2。采用FT-IR、PXRD、TGA及比表面积分析等技术对材料进行综合表征,并测定了 IPM-SIFSIX-2a对多种气体组分的吸附等温线。实验结果表明,IPM-SIFSIX-2a对50:50 C2H2/C2H4、50:50C2H2/CO2、50:50 CO2/CH4和 10:90C02/N2 的 IAST 吸附选择性分别达到了 8.3,5.3,62.3 和 72.4。其中 IPM-SIFSIX-2a 对 C2H2/C2H4和 CO2/CH4的吸附选择性均为目前SOFs中最高。相比IPM-SIFSIX-1a,IPM-SIFSIX-2a对C2H2有更低的等量吸附热(15.3kJ/mol)表明IPM-SIFSIX-2a用于气体吸附相较其它材料需要较少的再生能量。
[Abstract]:Adsorption separation is a very important technology of chemical separation process, its core is the development of efficient adsorption separation materials. Metal organic frameworks (Metal, organic frameworks, MOFs) and covalent organic frameworks (Covalent, organic frameworks, COFs) as a new type of porous materials with high specific surface area, pore size and relatively stable performance adjustable advantages for adsorption and separation technology can replace traditional potential. The supramolecular organic framework materials (Supramolecular organic frame works, SOFs) compared with MOFs and COFs, with low density, high flexibility, easy purification and regeneration etc., but because of its relatively weak non covalent network structure makes it difficult to remain stable and less for adsorptive separation. Organic complexes of adenine with metal ions as building units, for the preparation of SOFs materials with the advantages of MOFs and SOFs in this paper. Design of adenine SOFs, discuss the synthesis and its application in adsorption of low carbon hydrocarbons, for the development of new materials for adsorption and separation has important scientific research value, but also provides a new idea and reference for light hydrocarbon separation. Firstly, porous hydrogen bonded supramolecular organic framework materials synthesized by MPM-1-Br. Slow diffusion, MPM-1-Cl and MPM-1-TIFSIX. by SEM, PXRD, TGA and specific surface area analysis, comprehensive characterization of material technology, and the determination of three kinds of homogeneous porous hydrogen bonded supramolecular organic framework materials on the isothermal adsorption of gas acetylene and two carbon oxide single group. Experimental results show that MPM-1-Br, MPM-1-Cl and MPM-1-TIFSIX surface the area was 373 M2 - g-1417 M2 - g-1 and 1020 M2 g-1 respectively, and had good stability in the temperature range of 240 DEG and 200 DEG C; at 298 K and a total pressure of 100 kPa. IAST calculated the adsorption selectivity of 50:50 C2H2/CO2 before the two mixed gas respectively reached 3.8 and 3, and HKUST-1 (4.7) and UTSA-30 (3.3) and other metal organic framework materials have considerable separation performance. Secondly, by changing the ion type, new porous hydrogen bonded supramolecular organic framework materials IPM-SIFSIX-1. by SXRD, the the synthesis of PXRD, optical microscopy, and TGA surface area analysis and comprehensive characterization of material technology, and determination of IPM-SIFSIX-1 on the adsorption isotherms of various gases. The experimental results show that the specific surface area of IPM-SIFSIX-1 339m2 g-1, and has the hydrothermal stability; at 298 K and a total pressure of 100kPa for selective adsorption 50:50C2H2/C2H4,50:50C2H2/CO2 and 10:90CO2/N2 mixed gas respectively reached 7.1,4.9 and 97. of its 50:50 C2H2/C2H4 selectivity in SOFs after HOF-1 (7.4) in Zi Yanshe. The experimental results show that the performance of C2H2 and IPM-SIFSIX-1a both have high adsorption selectivity to C2H2/C2H4 can form a relatively strong hydrogen bonding interaction with IPM-SIFSIX-1a structure in SiF62-. Through the water immersion IPM-SIFSIX-1a solution structure collapse or (NH4) 2SiF6 water solution, we found that IPM-SIFSIX-1 has a self recovery performance. Finally, based on the separation performance of IPM-SIFSIX-1 with superior gas adsorption, through further modification of ligand structure, porous hydrogen bonded supramolecular organic framework materials IPM-SIFSIX-2. by FT-IR, the synthesis of PXRD, TGA and the ratio of surface integral analysis technology comprehensive characterization of the materials, and determination of IPM-SIFSIX-2a on the adsorption isotherms of various gases. The experimental results show that the IAST IPM-SIFSIX-2a 50:50 C2H2/C2H4,50:50C2H2/CO2,50:50 CO2/CH4 on selective adsorption and 10:90C02/N2 are 8.3,5.3,62.3 and 7 2.4. IPM-SIFSIX-2a of C2H2/C2H4 and the selective adsorption of CO2/CH4 were present in the highest SOFs. Compared to IPM-SIFSIX-1a, IPM-SIFSIX-2a to C2H2 a lower isosteric heat of adsorption (15.3kJ/mol) showed that IPM-SIFSIX-2a used in gas adsorption regeneration compared with other materials requires less energy.

【学位授予单位】：浙江大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ424;TQ028.15

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