以蒸气加工法制备和修饰金属-有机框架膜

doi:10.11949/0438-1157.20241225

摘要/Abstract

摘要：

金属-有机框架（MOF）是由金属离子或金属离子簇与有机配体配位连接而成的一类高度有序的多孔材料。作为分离膜材料具有广泛的应用潜力。开发高效的MOF膜制备和修饰方法对获得连续、致密、结构可调控的MOF膜至关重要。相比传统液相合成过程，蒸气加工方法可大幅节省溶剂及前体用量，有效避免竞争性体相成核，降低后处理过程中因溶剂分子移除造成的膜层开裂风险，兼具效率高和环境友好的特点。系统总结了蒸气加工法用于MOF膜的直接合成与合成后修饰改性方面的研究进展以及蒸气加工方法对MOF膜分离性能的调控和强化作用，并展望了蒸气加工法未来的发展方向及其在MOF膜放大制备方面的应用潜力。

关键词: 金属-有机框架, 膜, 蒸气加工, 直接合成, 合成后修饰, 分离, 渗透率, 选择性

Abstract:

Metal-organic frameworks (MOFs) are a class of highly ordered porous materials composed of metal ions or metal ion clusters coordinated with organic ligands. MOF membranes have been widely used in the chemical separation. High-efficient synthetic and post-synthetic modification methods help to obtain continouous, defect-free and structurally diverse MOF membranes. Compared with traditional liquid-phase synthesis methods, vapor processing is a high-effcient and environmentally friendly method. Using a vapor processing method, we can cut down the consumption of solvents and precursors, avoid the competitive nucleation in a bulk solution, reduce the risk of membrane cracking as a result of the removal of solvent molecules in the post-treatment of membranes. In this review, we summarize the research progress in direct synthesis and post-synthetic modifications of MOF membranes by vapor processing, and highlight the achivenments in regulation and optimization of membrane performances by vapor processing. Finally, an outlook on future directions of vapor processing and its potential for large-scale production of MOF membranes were provided.

Key words: metal-organic frameworks, membrane, vapor processing, direct synthesis, post-synthetic modification, separation, permeance, selectivity

中图分类号:

TQ 028.8

张耀辉, 班宇杰, 杨维慎. 以蒸气加工法制备和修饰金属-有机框架膜[J]. 化工学报, 2025, 76(5): 2070-2086.

Yaohui ZHANG, Yujie BAN, Weishen YANG. Vapor-phase synthesis and post-synthetic modification of metal-organic framework membranes[J]. CIESC Journal, 2025, 76(5): 2070-2086.

图/表 15

图1 以蒸气加工法制备和修饰MOF膜

Fig.1 Vapor-phase synthesis and post-synthetic modification of MOF membranes

图2 (a) 锌基凝胶的气-固相转化[52]；(b) ZIF-8中空纤维膜组件[52]；(c) 钴基凝胶的气-固相转化[53]

Fig.2 (a) Gas-solid phase transformation of zinc-based gel[52]; (b) A ZIF-8 hollow fibre membrane module[52]; (c) Gas-solid phase transformation of cobalt-based gel[53]

图3 (a) 不同反应时间晶间通道尺寸变化 (基于努森扩散原理计算)[54]；(b) 不同反应时间下膜的染料截留能力及乙醇透量[54]

Fig.3 (a) Variation of intercrystalline channel size at different reaction times (measured based on Knudsen diffusion principle) [54];(b) Dye retention performances and ethanol permeances of membrane at different reaction times[54](1 bar=0.1 MPa)

图4 (a) 电子束诱导氧化锌区域选择性转化为ZIF-8示意图[62]；(b) 图案化ZIF-8的原子力显微镜图像[62]

Fig.4 (a) Schematic illustration of e-beam-induced area-selective transformation of ZnO into ZIF-8[62]; (b) Atomic force microscope image of patterned ZIF-8[62]

图5 (a) ZnO的ALD沉积与气-固相转化[63]；(b) γ-Al2O3载体、ZnO层、ZIF-8膜的截面元素分布图[63]；(c) ALD循环次数对气-固相转化前后膜的丙烯渗透率与丙烯/丙烷选择性的影响[63]

Fig.5 (a) Schematic illustration of deposition of ZnO film through ALD and its further vapor transformation[63]; (b) Elemental distributions along cross sections of γ-Al2O3 support, ZnO film and ZIF-8 membrane[63]; (c) Influence of ALD cycles on propylene permeance and propylene/propane selectivity[63]

图6 (a) 固态溶剂策略制备混合基质膜；(b) CuSiF6@PEG前体的高分辨透射电子显微镜图像[64]；(c) Cu(SiF6)(bpy)2@PEG混合基质膜的高分辨透射电子显微镜图像[64]；(d) 不同MOF负载量的传质示意图[64]；(e) MOF负载量与金属盐转化率的对应关系（Mw代表聚合物分子量）[64]；(f) H2/CO2分离性能与文献对比[64]

Fig.6 (a) Mixed-matrix membrane (MMM) fabricated by a solid-solvent processing strategy[64]; (b) High-resolution transmission electron microscope image of the Cu(SiF6)(bpy)2@PEG MMM[64]; (c) High-resolution transmission electron microscope image of the Cu(SiF6)(bpy)2@PEG MMM[64]; (d) Schematic illustration of mass-transfer through MMM with different MOF loadings (Mw stands for the molecular mass of polymer) [64]; (e) MOF loadings varied with metal salt conversion ratios[64]; (f) Comparison of H2/CO2 separation performances between Cu(SiF6)(pyz)3@polymer MMMs and other membranes in literature[64]

图7 (a) 扫描电子显微镜和略入射X射线衍射表征不同溶剂量对膜的表面形貌和结晶性的影响（红色线、黑色线分别代表实验和模拟谱图）[65]；(b) 溶剂对气-固反应产物的影响[66]

Fig.7 (a) Influence of different template amounts on film morphology (characterized by scanning electron microscope) and crystallinity (characterized by grazing incidence X-ray diffraction), red and black lines represent experimental and simulated patterns, respectively[65]; (b) Effect of solvent on topologies of products[66]

图8 前体溶液的浸渍与溶剂蒸气辅助转化[69]

Fig.8 Dip-coating of precursor solution and solvent vapor-assisted transformation[69]

图9 (a) Cu3(C6O6)2的一步全气相转化策略[70]；(b) 双加热气相转化系统[71]

Fig.9 (a) Single-step all-vapor-phase conversion strategy for Cu3(C6O6)2[70]; (b) A typical vapor conversion device with dual heating zones[71]

图10 (a) ZIF-8的气相配体置换过程示意图[73]；(b) 置换比例随时间的变化 (蓝色线、绿色线、橙色线分别代表粒径为90 nm、15 μm、150 μm的ZIF-8)[73]；(c) ZIF-8的二次气相配体置换示意图[74]

Fig.10 (a) Schematic illustration of vapor-phase linker exchange process of ZIF-8[73]; (b) Vapor-phase linker exchange ratio as a function of time (blue, green, and orange lines represent ZIF-8 particles with sizes of 90 nm, 15 μm, and 150 μm, respectively ) [73]; (c) Schematic illustration of the secondary vapor-phase linker exchange process of ZIF-8[74]

图11 (a) ZIF-8膜的气相配体置换与孔径变化[75]；(b) 配体置换后膜的单组分气体渗透行为变化[75]；(c) 配体置换后膜的选择性变化[75]；(d) 部分无定形ZIF-8膜的制备示意图[76]；(e) 具有晶间缺陷的多晶膜与部分无定形膜的气体传输路径示意图[76]；(f) 配体置换后膜的选择性变化[76]

Fig.11 (a) Vapor-phase linker exchange process of ZIF-8 membrane and its pore size variation[75]; (b) Gas permeation properties of membrane after linker exchange[75]; (c) Permselectivity of gas pairs before and after linker exchange[75]; (d) Schematic of preparation of partially amorphous ZIF-8 membrane[76]; (e) Schematic of gas transport through polycrystalline membranes with grain boundary defects and partially amorphous membrane[76]; (f) Permselectivity of gas pairs before and after linker exchange[76](1 Å=0.1 nm)

图12 (a) 升降温过程中分子守门员质心距离与相应孔径变化[77]；(b) 升温后的气体渗透特性[77]；(c) 升降温循环下膜的稳定性[77]

Fig.12 (a) Change in centroid distance of molecular gatekeepers during a heating-cooling cycle and corresponding pore size evolutions[77]; (b) Gas permeation properties varied with temperatures[77]; (c) Stability of membrane during a heating-cooling cycle[77]

图13 蒸气诱导ZIF-108拓扑结构可逆转变示意图[80]

Fig.13 Schematic of vapor-induced reversible topological transformation of ZIF-108[80]

图14 (a) 以Mn(acac)2蒸气处理ZIF-8膜示意图[81]；(b) 蒸气处理前后O、Zn、N、Mn的比例变化(X射线光电子能谱表征) [81]；(c) 气相处理前后的气体渗透行为[81]

Fig.14 (a) Schematic illustration of treatment of ZIF-8 using Mn(acac)2 vapor[81]; (b) Ratio of integrated area of O, Zn, N, and Mn for ZIF-8 films before and after Mn(acac)2 treatment (characterized by X-ray photoelectron spectroscopy) [81]; (c) Permselectivity of gas pairs before and after vapor-treatment[81]

图15 (a) 甲酸蒸气诱导NU-906原位重结晶示意图[82]；(b) 不同反应时间对表面形貌的影响[82]；(c) 不同时间的甲酸蒸气处理后接触角的变化[82]；(d) 正丁醇/水的渗透气化性能[82]

Fig.15 (a) Schematic illustration of fabrication process of NU-906 membrane by in situ recrystallization under formic acid vapor[82]; (b) Effect of different reaction times on membrane surface morphology[82]; (c) Variation of contact angles over vapor treatment times[82]; (d) Pervaporation performance of NU-906 film for n-butanol/water feed solution[82]

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