金属有机化合物IRMOF-3、ZIF-7的制备及成膜研究
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摘要
金属-有机骨架材料(MOFs)作为一种新型的无机多孔材料,因其优异的性能使其得到国际材料学、化学与物理学界的高度重视,并迅速发展成为跨学科的研究热点之一,作为功能材料在选择性催化、气体吸附、光电材料和磁性材料等领域显示了迷人的应用前景,也成为了新一代优异的膜材料。在气体分离如H2/CH4、O2/N2、CO2/CH4分离及手性催化分离等方面具有潜在的用途,其晶体的制备及成膜化均具有重要的科学研究价值及潜在的工业应用价值。目前金属有机骨架材料(MOFs)的成膜化研究刚刚起步,很多机理及条件还不完善,使得这种材料的成膜化尤其是在管状载体上的成膜化研究成为一大热点及难点。
本文研究了IRMOF-3晶体合成的反应条件对晶体形貌、结构等物理化学性能的影响,利用SEM、XRD进行表征分析。研究结果表明：在Zn2+:ABDC= 2:1、403 K下制备的晶体结晶度较高,并通过对加热方式的考察,确定微波加热可以有效减小晶粒尺寸,同时将制备时间缩短至30 min。其次开展了在α-Al203管状载体上IRMOF-3的成膜研究,实验结果表明,用微波辅助晶种法在CZn2+= 0.05 mol/L时制备的IRMOF-3膜层较连续,经过重复合成,能有效提高膜层质量,在0.1MPa测试压力下氢气渗透速率为4.39×10-7 mol/m2·s·Pa, H2/CO2、H2/N2、H2/CH4分离比分别达到4.12、3.48、2.56,接近努森扩散值。
鉴于IRMOF-3膜的性能还不完善,在实验的基础上,选取孔径为3(?)的ZIF-7体系,对其进行了晶体制备及成膜研究,创新性的用动态晶化的方法,在Zn2+：BIM=1：2.,CZn2+= 0.05 mol/L,393 K的条件下晶化120 min制备出了与载体相匹配的晶体作为二次生长的晶种。然后用微波辅助的二次生长法,将成膜时间缩短至30 min,通过重复合成,提高膜层质量,其氢气渗透速率为8.93×10-7 mol/m2·s·Pa, H2/N2、H2/CO2、H2/CH4的理想分离比也分别达到了4.04、4.86、2.05。
Metal-Organic Frameworks (MOFs) as a new inorganic porous material, because of their excellent performance catch much attention in the international materials science, chemistry and physics, and quickly developed into one of the hot cross-disciplinary research. As an selective catalytic functional materials, MOFs shows a fascinating prospect in gas adsorption, optical materials and magnetic fields, also has become a new generation of excellent membrane material, in gas separation, such as H2/CH4, O2/N2, CO2/CH4 isolation and separation of chiral catalysis. Its preparation and made to membrane has great scientific values and potential industrial applications. At present, the study of the preparation of MOFs membrane has just started, many mechanisms and conditions are not perfect, makes it especiallyon the tubular carrier to be a research hot topic and difficulty.
In this paper, we studied the influence of synthesis reaction conditions of IRMOF-3 crystal on the crystal morphology, structure and other physical chemical properties, used SEM, XRD to characterize the results. Studies have shown that:IRMOF-3 crystals which showed higher crystallinity were obtain under the following conditions:Zn2+:ABDC=2:1, synthesis temperature of 403 K. Through the study of heating, proved that IRMOF-3 crystals whose crystal particles were smaller and more uniform, were obtained under the microwave heating used only 30 min. Then we carried out the preparation of IRMOF-3 membrane onα-Al2O3 tubular carrier, the experimental results show that, used the microwave-assisted seed method get more continuous film at CZn2+= 0.05 mol/L, after repeated synthesis, can effectively improve the film quality, at 0.1 MPa psid hydrogen penetration rate of 4.39×10-7 mol/m2·s·Pa, the separation ratio of H2/CO2, H2/N2, H2/CH4 were 4.12,3.48,2.56, close to Knudsen diffusion value.
In view of IRMOF-3 membrane performance was not perfect, based on experiment, we selected the ZIF-7 system whose aperture was about 3 A, carried out the preparation of crystal and membrane. We prepared out the crystal which matched carrier can used as the seed of secondary growth with dynamic crystallization method, under the following conditions: synthesis temperature of 393 K, reaction time of 120 min, and Zn2+:BIM= 1:2.8, CZn2+= 0.05 mol/L. Then use microwave-assisted seed method reduced the preparation time to 30 min, through repeated synthesis, improve the coating quality, the hydrogen penetration rate of 8.93×10-7 mol/m2·s·Pa, and the ideal separation ratio of H2/N2,H2/CO2,H2/CH4 achieved respectively to 4.04,4.86,2.05.
本文研究了IRMOF-3晶体合成的反应条件对晶体形貌、结构等物理化学性能的影响,利用SEM、XRD进行表征分析。研究结果表明：在Zn2+:ABDC= 2:1、403 K下制备的晶体结晶度较高,并通过对加热方式的考察,确定微波加热可以有效减小晶粒尺寸,同时将制备时间缩短至30 min。其次开展了在α-Al203管状载体上IRMOF-3的成膜研究,实验结果表明,用微波辅助晶种法在CZn2+= 0.05 mol/L时制备的IRMOF-3膜层较连续,经过重复合成,能有效提高膜层质量,在0.1MPa测试压力下氢气渗透速率为4.39×10-7 mol/m2·s·Pa, H2/CO2、H2/N2、H2/CH4分离比分别达到4.12、3.48、2.56,接近努森扩散值。
鉴于IRMOF-3膜的性能还不完善,在实验的基础上,选取孔径为3(?)的ZIF-7体系,对其进行了晶体制备及成膜研究,创新性的用动态晶化的方法,在Zn2+：BIM=1：2.,CZn2+= 0.05 mol/L,393 K的条件下晶化120 min制备出了与载体相匹配的晶体作为二次生长的晶种。然后用微波辅助的二次生长法,将成膜时间缩短至30 min,通过重复合成,提高膜层质量,其氢气渗透速率为8.93×10-7 mol/m2·s·Pa, H2/N2、H2/CO2、H2/CH4的理想分离比也分别达到了4.04、4.86、2.05。
Metal-Organic Frameworks (MOFs) as a new inorganic porous material, because of their excellent performance catch much attention in the international materials science, chemistry and physics, and quickly developed into one of the hot cross-disciplinary research. As an selective catalytic functional materials, MOFs shows a fascinating prospect in gas adsorption, optical materials and magnetic fields, also has become a new generation of excellent membrane material, in gas separation, such as H2/CH4, O2/N2, CO2/CH4 isolation and separation of chiral catalysis. Its preparation and made to membrane has great scientific values and potential industrial applications. At present, the study of the preparation of MOFs membrane has just started, many mechanisms and conditions are not perfect, makes it especiallyon the tubular carrier to be a research hot topic and difficulty.
In this paper, we studied the influence of synthesis reaction conditions of IRMOF-3 crystal on the crystal morphology, structure and other physical chemical properties, used SEM, XRD to characterize the results. Studies have shown that:IRMOF-3 crystals which showed higher crystallinity were obtain under the following conditions:Zn2+:ABDC=2:1, synthesis temperature of 403 K. Through the study of heating, proved that IRMOF-3 crystals whose crystal particles were smaller and more uniform, were obtained under the microwave heating used only 30 min. Then we carried out the preparation of IRMOF-3 membrane onα-Al2O3 tubular carrier, the experimental results show that, used the microwave-assisted seed method get more continuous film at CZn2+= 0.05 mol/L, after repeated synthesis, can effectively improve the film quality, at 0.1 MPa psid hydrogen penetration rate of 4.39×10-7 mol/m2·s·Pa, the separation ratio of H2/CO2, H2/N2, H2/CH4 were 4.12,3.48,2.56, close to Knudsen diffusion value.
In view of IRMOF-3 membrane performance was not perfect, based on experiment, we selected the ZIF-7 system whose aperture was about 3 A, carried out the preparation of crystal and membrane. We prepared out the crystal which matched carrier can used as the seed of secondary growth with dynamic crystallization method, under the following conditions: synthesis temperature of 393 K, reaction time of 120 min, and Zn2+:BIM= 1:2.8, CZn2+= 0.05 mol/L. Then use microwave-assisted seed method reduced the preparation time to 30 min, through repeated synthesis, improve the coating quality, the hydrogen penetration rate of 8.93×10-7 mol/m2·s·Pa, and the ideal separation ratio of H2/N2,H2/CO2,H2/CH4 achieved respectively to 4.04,4.86,2.05.
引文
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