Preparation and gas separation properties of fluorinated covalent organic frameworks/polyimide mixed matrix membranes
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摘要: 混合基质膜结合聚合物膜的柔韧性和多孔填料的气体分离性能，近年来在气体分离领域被广泛关注。共价有机框架材料(COFs)具有高比表面积、高孔隙率、易功能化等特点，其全有机的结构展现出与聚合物之间良好的相容性，被认为是混合基质膜理想填料之一。因此，本研究通过溶剂热法合成了氟化共价有机框架材料TpPa-CF3，采用共混法以TpPa-CF3为填料，聚酰亚胺6FDA-ODA为基体制备TpPa-CF3/6FDA-ODA混合基质膜。通过傅里叶红外光谱(FT-IR)、X-射线衍射(XRD)、热重分析(TGA)、扫描电子显微镜(SEM)和气体渗透性等测试对TpPa-CF3及其混合基质膜进行结构与性能的研究。结果表明，TpPa-CF3均一的孔道为气体分子传输提供了快速通道，框架的微孔结构增强了气体分子与孔壁上功能基团的相互作用。当TpPa-CF3负载量为5 wt%时，CO2和O2渗透性相较于6FDA-ODA基体膜分别提高了149%和138%，CO2/N2和O2/N2分离因子分别提升到24.4和4.8。Abstract: Mixed matrix membranes, which combine the flexibility of polymer membranes with the gas separation properties of porous fillers, have attracted much attention in the field of gas separation in recent years. Covalent organic framework materials (COFs) are distinguished by a high specific surface area, high porosity, and facile functionalization. Their all-organic structure exhibits favorable compatibility with polymers, which is regarded as an optimal filler for mixed matrix membranes. Accordingly, in this study, the fluorinated covalent organic framework material TpPa-CF3 was synthesized via a solvothermal method, and TpPa-CF3/6FDA-ODA mixed matrix membranes were prepared through a blending method utilizing TpPa-CF3 as a filler and polyimide 6FDA-ODA as a matrix. The structure and properties of TpPa-CF3 and its mixed matrix membranes were investigated through a series of analytical techniques, including FT-IR, XRD, TGA, SEM, and gas permeability tests. The results showed that the homogeneous pores of TpPa-CF3 provided fast channels for gas molecule transport, the microporous structure of the framework enhanced the interaction of gas molecules with functional groups on the pore walls, and the dipole-quadrupole interactions of C—F bonds with CO2 elevated the interactions of the framework with CO2. At a loading of 5 wt% of TpPa-CF3, the CO₂ and O₂ permeability exhibited an improvement of 149% and 138%, respectively, in comparison to the 6FDA-ODA matrix membrane. Additionally, the CO₂/N₂ and O₂/N₂ separation factors were elevated to 24.4 and 4.8, respectively.
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图 1 TpPa-CF3的(a)PXRD精修谱图(b)FT-IR谱图(c)13C固体核磁谱图
Figure 1. (a) PXRD refined spectra (b) FT-IR spectra (c) 13C solid-state NMR spectrum of TpPa-CF3
图 2 TpPa-CF3的XPS(a)全谱；(b)C 1 s；(c)N 1 s；(d)F 1 s
Figure 2. XPS spectra of TpPa-CF3 (a) Survey spectrum; (b) C 1 s; (c) N 1 s; (d) F 1 s
图 3 TpPa-CF3的(a)微观形貌(b)N2吸附-脱附曲线(c)孔径分布图(d)TGA和DTG曲线
Figure 3. (a) Microscopic morphology (b) N2 adsorption-desorption curves (c) Pore size distribution (d) TGA and DTG curves of TpPa-CF3
图 4 6 FDA-ODA及TpPa-CF3/6 FDA-ODA混合基质膜的(a)XRD曲线(b)FT-IR图谱
Figure 4. (a) XRD curves (b) FT-IR patterns of 6 FDA-ODA and TpPa-CF3/6 FDA-ODA mixed matrix membranes
图 5 6 FDA-ODA和TpPa-CF3/6 FDA-ODA混合基质膜的(a)TGA曲线(b)DSC曲线
Figure 5. (a) TGA curves (b) DSC curves of 6 FDA-ODA and TpPa-CF3/6 FDA-ODA mixed matrix membranes
图 6 膜表面和截面的SEM图像(a1-e1)膜表面；(a2-e2)膜截面(a-e分别代表不同TpPa-CF3的负载量：0，1，3，5，7 wt%)
Figure 6. SEM images of membrane surface and cross-section (a1-e1) membrane surface; (a2-e2) membrane cross-section (a-e represent different TpPa-CF3 loadings: 0, 1, 3, 5, 7 wt%, respectively)
图 7 不同负载量下TpPa-CF3/6 FDA-ODA混合基质膜的(a)接触角(b)应力-应变曲线
Figure 7. (a) Contact angle (b) Stress-strain curves of TpPa-CF3/6 FDA-ODA mixed matrix membranes at different loadings
图 8 不同负载量下TpPa-CF3/6 FDA-ODA混合基质膜的(a)气体渗透性(b)气体选择性(c)72 h 连续渗透性测试
Figure 8. (a) Gas permeability (b) Gas selectivity (c) 72 h continuous permeability performance test of TpPa-CF3/6 FDA-ODA mixed matrix membranes at different loadings
图 9 不同负载量的TpPa-CF3/6 FDA-ODA混合基质膜(a)CO2/N2(b)O2/N2的Robeson上限图
Figure 9. Robeson upper bound plots of TpPa-CF3/6 FDA-ODA mixed matrix membranes with different loadings (a) CO2/N2 (b) O2/N2
表 1 不同负载量下TpPa-CF3/6 FDA-ODA混合基质膜的力学性能
Table 1. Mechanical properties of TpPa-CF3/6 FDA-ODA mixed matrix membranes at different loadings
TpPa-CF3 Loadings/wt% Tensile Strength/MPa Elongation at Break/% Young’s Modulus/GPa θw/(°) 0 74.1 10.1 1.59 79.9 1 79.6 9.7 1.63 81.4 3 82.9 8.6 1.70 83.1 5 93.0 7.8 1.82 84.1 7 84.5 7.3 1.76 89.1 
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表 2 6 FDA-ODA及TpPa-CF3/6 FDA-ODA混合基质膜的气体渗透系数和理想选择性
Table 2. Gas permeability coefficients and ideal selectivity of 6 FDA-ODA and TpPa-CF3/6 FDA-ODA mixed matrix membranes
Membranes Permeability/Barrer Ideal Selectivity α CO2 O2 N2 α(CO2/N2) α(O2/N2) 6 FDA-ODA 12.47 2.55 0.64 19.5 4.0 1%TpPa-CF3/6 FDA-ODA 16.91 3.76 0.98 17.2 3.8 3%TpPa-CF3/6 FDA-ODA 22.77 4.43 1.03 22.0 4.3 5%TpPa-CF3/6 FDA-ODA 31.08 6.08 1.27 24.5 4.8 7%TpPa-CF3/6 FDA-ODA 18.62 4.16 1.11 16.8 3.8 Note: 1 Barrer = 10−10 cm3(STP)·cm·cm−2s−1·cmHg−1; Ideal Selectivity α = P(A)/P(B), A and B are two different pure gases.
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表 3 文献中报道的混合基质膜气体分离性能与本工作的对比
Table 3. Comparison of gas separation performance of mixed matrix membranes reported in the literature with the present work
Membranes type P(CO2) P(O2) $ \alpha $(CO2/N2) $ \alpha $(O2/N2) References TpPa-1-nc/Pebax 21 Barrer - 72 - [26] COFp-PVAm 270 Barrer - 86 - [27] TpBD@PBI-BuI 14.8 Barrer - 23 - [28] ZIF-7-I/(BPDA/6 FDA-ODA) - 2.9 Barrer - 0.19 [29] PBI-PI-based Carbon 293.5 Barrer 93.1 Barrer 8.3 2.6 [30] 5%TpPa-CF3/6 FDA-ODA 31.08 Barrer 6.08 Barrer 24.4 4.8 This work Note: Pebax—Poly(ether-block-amide); PVAm—Polyvinylamine; PBI-BuI—Tert-butylpolybenzimidazole;
ZIF-7-I—Wide-Pore ZIF-7; PBI—Polybenzimidazoles; PI—Polyimide.
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