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Development of hydrogen-selective CAU-1 MOF membranes for hydrogen purification by ‘dual-metal-source’ approach

机译:通过“双金属源”方法开发用于氢纯化的氢选择性CAU-1 MOF膜

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摘要

Hydrogen provides reliable, sustainable, environmental and climatic friendly energy to meet world's energy requirement and it also has high energy density. Hydrogen is relevant to all of the energy sectors-transportation, buildings, utilities and industry. In all of these sectors, hydrogen-rich gas streams are needed. Thus, hydrogen-selective membrane technology with superior performances is highly demanded for separation and puri?cation of hydrogen gas mixtures. In this study, novel [Al4(OH)2(OCH3)4(H2N-BDC)3] xH2O (CAU-1) MOF membranes with accessible pore size of 0.38 nm are evaluated for this goal of hydrogen puri?cation. High-quality CAU-1 membranes have been successfully synthesized on a-Al2O3 hollow ceramic ?bers (HCFs) by secondary growth assisted with the homogenously deposited CAU-1 nanocrystals with a size of 500 nm as seeds. The energy-dispersive X-ray spectroscopy study shows that the HCFs substrates play dual roles in the membrane preparation, namely aluminum source and as a support. The crystals in the membrane are intergrown together to form a continuous and crack-free layer with a thickness of 4 mm. The gas sorption ability of CAU-1 MOF materials is examined by gas adsorption measurement. The isosteric heats of adsorption with average values of 4.52 kJ/mol, 12.90 kJ/mol, 12.82 kJ/mol and 27.99 kJ/mol are observed for H2, N2, CH4, and CO2 respectively, indicating different interactions between CAU-1 framework and these gases. As-prepared HCF supported CAU-1 membranes are tested by single and binary gas permeation of H2/CO2, H2/N2 and H2/CH4 at different temperatures, feed pressures and testing time. The permeation results show preferential permeance of H2 over CO2, N2, and CH4 with high separation factors of 12.34, 10.33, and 10.42 for H2/CO2, H2/N2, H2/CH4, respectively. The temperature, pressure and test time dependent studies reveal that HCFs supported CAU-1 membranes possess high stability, resistance to cracking, temperature cycling, high reproducibility, these of which combined with high separation ef?ciency make this type of MOF membranes are promising for hydrogen recycling from industrial exhausts.
机译:氢能提供可靠,可持续,环境和气候友好的能源,以满足世界对能源的需求,并且具有很高的能量密度。氢与交通,建筑,公用事业和工业等所有能源部门有关。在所有这些领域中,都需要富氢气流。因此,对于氢气混合物的分离和纯化,迫切需要性能优异的氢选择性膜技术。在这项研究中,新颖的[Al4(OH)2(OCH3)4(H2N-BDC)3] xH2O(CAU-1)MOF膜的可达0.38 nm的孔径被评估用于实现氢纯化的目标。高质量的CAU-1膜已经成功地在a-Al2O3空心陶瓷纤维(HCF)上合成,并通过均匀生长的500nm尺寸的CAU-1纳米晶体作为种子进行了二次生长。能量色散X射线光谱研究表明,HCF基质在膜制备中起着双重作用,即铝源和作为载体。膜中的晶体相互生长在一起,形成厚度为4 mm的连续无裂纹层。通过气体吸附测量来检查CAU-1 MOF材料的气体吸附能力。观察到H2,N2,CH4和CO2的吸附等构热分别为4.52 kJ / mol,12.90 kJ / mol,12.82 kJ / mol和27.99 kJ / mol,表明CAU-1构架和CAU-1构架之间的相互作用不同这些气体。通过在不同温度,进料压力和测试时间下,H2 / CO2,H2 / N2和H2 / CH4的单次和二次气体渗透测试制备的HCF负载的CAU-1膜。渗透结果表明,H2的渗透率优于CO2,N2和CH4,H2 / CO2,H2 / N2,H2 / CH4的分离系数分别为12.34、10.33和10.42。温度,压力和测试时间的相关研究表明,HCFs支撑的CAU-1膜具有高稳定性,抗裂性,温度循环性,高重现性,这些特性与高分离效率相结合使得这种类型的MOF膜有望用于从工业废气中回收氢气。

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