共价有机框架(COFs)膜以及其它多孔有机框架膜材料的制备

1. 共价有机框架（COFs）膜材料的制备

图1 (a)溶剂热法制备COF-5膜示意图; (b)COF-5膜材料的X-射线散射图[2]

图2 (a)液-液界面制备的COFs膜的平面结构图; (b)液-液界面制备联吡啶COF膜的示意图; (c)联吡啶COF膜的俯视和仰视的AFM图像[3]

图3 (a)COFs的合成及其孔径和堆积距离模型的示意图; (b)溶液浇铸法制备COF@PBI-BuI膜的示意图; (c)TpPa-1和TpBD@PBI-BuI膜的柔韧性的光学照片[8]

图4 (a)COF-气凝胶加工成自支撑膜的示意图; (b)制备二维亚胺基COF的结构图; (c)、(e)与(g)为材料的反射XRD; (d)、(f)与(h)为材料的透射XRD; 其中(c)和(d)为TAPB-BTCA-COF膜的XRD图; (e)与(f)为PPDA-BTCA-COF膜的PXRD图; (g)与(h)为TAPB-PDA-AGCOF膜的PXRD图[9](XRD图中: 红色线为薄膜的XRD峰，绿色线为气凝胶的XRD峰，蓝色线为模拟材料的XRD峰)

图5 (a)TpPa(OH)₂COF膜的制备工艺图; (b)该膜的XRD图; (c)该膜的SEM及光学照片[10]

2. 其它多孔有机框架膜材料的制备

图6 在Al₂O₃载体上制备MIL-53薄膜的示意图[16]

图7 (a)用于制备三嗪类多孔膜的腈类单体的优化结构; (b)4,4′-联苯二腈的三聚反应过程图; (c)合成的三嗪-框架基膜的光学照片，圆圈内显示的是多孔框架局部的片段[17]

图8 (a)制备MMMs膜的MTZ-PIM与表面改性的二氧化硅的结构图；(b) MMMs薄膜的光学照片左上: PIM-1膜; 右上: MTZ-PIM膜; 左下: MTZ-PIM/NP膜(10 wt%)[18]

参考文献：

[1] A. Cote, A. Benin, N. Ockwig, et al. Porous, Crystalline, Covalent Organic Frameworks [J]. Science, 2005, 310(5751): 1166-1170.

[2] J. Colson, A. Woll, A. Mukherjee, et al. Oriented 2D Covalent Organic Framework Thin Films on Single-Layer Graphene [J]. Science, 2011, 332(6026): 228-231.

[3] Q. Tran, H. Lee, N. Tran. Covalent Organic Frameworks: From Structures to Applications [J]. Polymers, 2023, 15(5): 1279.

[4] C. Zhang, B. Wu, M. Ma, et al. Ultrathin Metal/Covalent-Organic Framework Membranes towards Ultimate Separation [J]. Chemical Society Reviews, 2019, 48(14): 3811-3841.

[5] H. Wang, Z. Zeng, P. Xu, et al. Recent Progress in Covalent Organic Framework Thin Films: Fabrications, Applications and Perspectives [J]. Chemical Society Reviews, 2019, 48(2): 488-516.

[6] S. S. Yuan, X. Li, J. Y. Zhu, et al. Covalent Organic Frameworks for Membrane Separation [J]. Chemical Society Reviews, 2019, 48(10): 2665-2681.

[7] J. Colson, A. Woll, A. Mukherjee, et al. Oriented 2D Covalent Organic Framework Thin Films on Single-Layer Graphene [J]. Science, 2011, 332(6026): 228-231.

[8] B. Biswal, H. Chaudhari, R. Banerjee, et al. Chemically Stable Covalent Organic Framework (COF)-Polybenzimidazole Hybrid Membranes: Enhanced Gas Separation through Pore Modulation [J]. Chemistry of A European Journal, 2016, 22(14): 4695-4699.

[9] J. Martín-Illán, J. Suárez, J. Gómez-Herrero, et al. Ultralarge Free-Standing Imine-Based Covalent Organic Framework Membranes Fabricated via Compression [J]. Advanced Science, 2022, 9(7): 2104643.

[10] J. Li, H. Rong, Y. Chen, et al. Screen Printing Directed Synthesis of Covalent Organic Framework Membranes with Water Sieving Property [J]. Chemical Communications, 2020, 56(48): 6519-6522.

[11] S. Hermes, F. Schroder, R. Chelmowski, et al. Selective Nucleation and Growth of Metal-Organic Open Framework Thin Films on Patterned COOH/CF3-Terminated Self-Assembled Monolayers on Au (111) [J]. Journal of the American Chemical Society, 2005, 127(40): 13744-13745.

[12] M. Arnold, P. Kortunov, D. Jones, et al. Oriented Crystallisation on Supports and Anisotropic Mass Transport of the Metal‐Organic Framework Manganese Formate [J]. European Journal of Inorganic Chemistry, 2007,1, 60-64.

[13] E. Biemmi, C. Scherb and T. Bein. Oriented Growth of the Metal Organic Framework Cu₃(BTC)₂(H₂O)₃ˑxH₂O Tunable with Functionalized Self-Assembled Monolayers [J]. Journal of the American Chemical Society, 2007, 129(1): 8054- 8055.

[14] C. Scherb, A. Schodel, T. Bein. Directing the Structure of Metal-Organic Frameworks by Oriented Surface Growth on an Organic Monolayer [J]. Angewandte Chemie International Edition, 2008, 47(31): 5777-5779.

[15] J. Gascon, S. Aguado F. Kapteijn. Manufacture of Dense Coatings of Cu₃(BTC)₂(HKUST-1) on α-alumina [J]. Microporous Mesoporous Materials, 2008, 113(1- 3): 132-138.

[16] Y. Hu, X. Dong, J. Nan, et al. Metal–Organic Framework Membranes Fabricated via Reactive Seeding [J]. Chemical Communication, 2011, 47(2): 737-739.

[17] X. Zhu, C. Tian, S. Mahurin. A Superacid-Catalyzed Synthesis of Porous Membranes Based on Triazine Frameworks for CO2 Separation [J]. Journal of the American Chemical Society, 2012, 134(25): 10478-10484.

[18] A. Imai, H. Mikami, E. Ito, et al. Influence of Chemical Modification on CO₂ Permeability of Polymers of Intrinsic Microporosity/Silica Nanoparticles Composite Membranes [J]. Journal of Photopolymer Science and Technology, 2019, 32(3): 457-461.

我喜欢向日葵，它开花的时候，无论昨夜经历怎样的风雨，当清晨的第一缕阳光来临时它还是努力的抬起头向着阳光，并一路坚强勇敢的追逐着阳光，开出一片灿烂的金黄。

有趣的灵魂在等你

长按扫码可关注

伍