物理化学学报 >> 2020, Vol. 36 >> Issue (1): 1901079.doi: 10.3866/PKU.WHXB201901079

所属专题： 庆祝唐有祺院士百岁华诞专刊

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聚合物支撑的金属有机骨架膜的制备及其气体分离性能

付静茹1,贲腾1,裘式纶2,*()   

  1. 1 吉林大学, 化学学院，长春 130012
    2 吉林大学，无机合成与制备化学国家重点实验室，长春 130012
  • 收稿日期:2019-01-29 录用日期:2019-02-26 发布日期:2019-03-06
  • 通讯作者: 裘式纶 E-mail:sqiu@jlu.edu.cn
  • 基金资助:
    国家自然科学基金(21390394);国家自然科学基金(21471065);国家自然科学基金(21871103);吉林省科技发展计划项目(20180414009GH)

Fabrication of Polymer-Supported Metal Organic Framework Membrane and Its Gas Separation Performance

Jingru Fu1,Teng Ben1,Shilun Qiu2,*()   

  1. 1 College of Chemistry, Jilin University, Changchun 130012, P. R. China
    2 State Key Laboratory of Inorganic Synthesis and Preparation Chemistry, Jilin University, Changchun 130012, P. R. China
  • Received:2019-01-29 Accepted:2019-02-26 Published:2019-03-06
  • Contact: Shilun Qiu E-mail:sqiu@jlu.edu.cn
  • Supported by:
    the National Natural Science Foundation of China(21390394);the National Natural Science Foundation of China(21471065);the National Natural Science Foundation of China(21871103);the Science and Technology Department of Jilin Province Foundation, China(20180414009GH)

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摘要：

由于MOF (金属有机骨架)膜与基底之间的作用力较薄弱，所以制备具有高的H2渗透性和H2/CO2选择性的致密连续的大面积金属有机骨架膜仍具有巨大挑战。本文选取多孔Al2O3作为基底，在表面涂覆一层PIM-1 (一种固有微孔聚合物)，并对其进行羧基化处理，使得表面具有大量的羧基基团，随后利用羧基与金属之间的相互作用，原位生长得到了两种致密连续的聚合物支撑的MOF膜(PIM-1-COOH/ZIF-8和PIM-1-COOH/HKUST-1)。通过XRD的表征可以看出MOF膜是纯相的并且具有较高的结晶性；SEM的测试结果表明MOF膜是致密连续的并且MOF膜与基底之间紧密结合。气体分离测试结果表明，这两种MOF膜对H2具有较高的渗透性以及H2/CO2选择性。在常温常压下，对于PIM-1-COOH/ZIF-8和PIM-1-COOH/HKUST-1膜，H2/CO2双组分气体的分离系数分别为7.32、9.69，并且它们H2的渗透通量分别高于3.16 × 10-6、1.14 × 10-6 mol·m-2·s-1·Pa-1。在单组份测试中，这两种MOF膜的H2/CO2的理想分离系数分别为7.70、12.04；H2的渗透通量分别高达3.73 × 10-6、3.86 × 10-6 mol·m-2·s-1·Pa-1，这就表明这两种MOF膜有望在H2的纯化和分离方面广泛应用。

关键词: 膜, 聚合物, 金属有机骨架, 气体分离, 氢气纯化

Abstract:

The fabrication of compact, continuous, and large-scale metal organic framework (MOF) membranes with high permeability and H2/CO2 selectivity remains challenging because of the wake interaction between the MOF membrane and the substrate. In addition, substrates with smooth and plain surfaces and suitable pore size are required to prepare high-quality MOF membranes because it is difficult to obtain dense and continuous MOF membranes on a substrate with large pores and rough surfaces. To overcome these challenges, numerous MOF membrane growth methods have emerged, including in situ (direct) growth, secondary (seeded) growth, and layer-by-layer growth methods as well as electrostatic spinning and the chemical modification of the substrate. Among these methods, usage of substrates suitable for surface-functionalization is a promising technique. Herein, Al2O3 was selected as the substrate and was coated with PIM-1 (one polymer of intrinsic microporosity), followed by carboxylation of PIM-1 to furnish a large number of carboxyl groups on the surface. In situ growth of the MOF membrane using the interactions between the carboxyl group and the metal yielded two types of compact, continuous, and large-scale polymer-supported MOF membranes (PIM-1-COOH/ZIF-8 and PIM-1-COOH/HKUST-1). Furthermore, the fabricated polymer-supported MOF membrane structures were investigated by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). Gas separation experiments were performed to explore the gas permeability and selectivity of the prepared MOF membranes. The XRD characterization confirmed the pure phase and high crystallinity of the MOF membranes. The SEM images showed that the MOF membranes were compact and continuous with a tight combination between the MOF crystal membrane and the substrate. Gas separation measurements showed that both MOF membranes exhibited high H2 permeability and selectivity for H2/CO2. For the PIM-1-COOH/ZIF-8 and PIM-1-COOH/HKUST-1 membranes, the 1 : 1 binary mixtures gas separation factors of H2/CO2 calculated as the gas molar ratios in the permeate and retentate side 7.32 and 9.69, respectively, at room temperature and atmospheric pressure. The H2/CO2 mixture separation factors of the two MOF membranes exceeded the corresponding Knudsen constants (4.7), with H2 permeances higher than 3.16 × 10-6 and 1.14 × 10-6 mol·m-2·s-1·Pa-1, respectively. The ideal separation factors of H2/CO2 of both MOF membranes calculated as the ratio of single gas permeances were 7.70 and 12.04, respectively, with the respective H2 permeances of up to 3.73 × 10-6 and 3.86 × 10-6 mol·m-2·s-1·Pa-1. Because of their outstanding characteristics, these novel MOF membranes can be widely used in the fields of H2 purification and separation.

Key words: Membrane, Polymer, Metal organic frameworks, Gas separation, Hydrogen purity