连续ZIF-8膜制备及在氢气分离中的研究进展

doi:10.16085/j.issn.1000-6613.2024-0551

化工进展 ›› 2024, Vol. 43 ›› Issue (S1): 403-418.DOI: 10.16085/j.issn.1000-6613.2024-0551

连续ZIF-8膜制备及在氢气分离中的研究进展

谢钰麟¹(), 饶瑞晔²(), 黄建¹, 蒿佳怡¹, 王友益¹, 黄琦¹

^1.福州大学环境与安全工程学院，福建福州 350001
^2.武夷学院绿色化工技术福建省高等学校重点实验室，生态与资源工程学院，福建武夷山354300

收稿日期:2024-04-03 修回日期:2024-06-28 出版日期:2024-11-20 发布日期:2024-12-06
通讯作者: 饶瑞晔
作者简介:谢钰麟（1998—），男，硕士研究生，研究方向为MOF膜用于气体分离。E-mail：1538206952@qq.com。
基金资助:
国家自然科学基金(51406141);福建省科技厅自然科学基金（2024J01919,闽财指[2023]893号）;福建省南平市科技计划(N2021Z015);武夷学院经费项目(KC202224SC)

Preparation of continuous ZIF-8 membrane and its progress in hydrogen separation

XIE Yulin¹(), RAU Jui-yeh²(), HUANG Jian¹, HAO Jiayi¹, WANG Youyi¹, HUANG Qi¹

^1.College of Environment and Safety, Fuzhou University, Fuzhou 350001, Fujian, China
^2.Key Laboratory of Green Chemical Technology of Fujian Province University, College of Ecology and Resources Engineering, Wuyi University, Wuyishan 354300, Fujian, China

Received:2024-04-03 Revised:2024-06-28 Online:2024-11-20 Published:2024-12-06
Contact: RAU Jui-yeh

摘要/Abstract

摘要：

ZIF-8膜是一种新型的金属有机框架材料纳米多孔材料。由于其独特的蜂窝状多孔结构以及优良的热稳定性和化学稳定性，近年来在气体分离领域得到了广泛应用。ZIF-8膜的孔径介于氢气和其他气体（如氮气、甲烷等）的动力学直径之间，使其特别适合用于氢气的分离。本文综述了连续ZIF-8膜的制备方法，重点介绍了近十年来有代表性的原位生长法、二次晶种法、表面修饰法和一些特殊的制备方法。整理并比较了这些方法所制备的连续ZIF-8膜的氢气分离性能以及各方法的优缺点。同时，对原位生长法、二次晶种法和表面修饰法的合成机理进行了详细总结。此外，还简要讨论了未来的研究方向和挑战。

关键词: 连续ZIF-8膜, 氢气分离, 原位生长法, 二次晶种法, 载体表面修饰法

Abstract:

The ZIF-8 membrane represents a novel class of metal-organic framework (MOF) materials characterized by nanoporous structure. Due to its distinctive honeycomb-like porous structure and remarkable thermal and chemical stability, ZIF-8 membranes have gained significant traction in the field of gas separation in recent years. The pore size of ZIF-8 membranes lies between the kinetic diameters of hydrogen and other gases (e.g., N₂, CH₄, etc.), rendering them particularly suited for the separation of hydrogen. This paper reviewed the preparation methods of continuous ZIF-8 membranes with a focus on the in-situ growth method, the secondary crystal seeding method, the surface modification method and some special preparation methods that were represented in the last decade. This review presented a comparative analysis of the hydrogen separation performance of continuous ZIF-8 membranes prepared by the aforementioned methods along with an evaluation of the advantages and disadvantages associated with each method. In parallel, the synthesis mechanisms of the in-situ growth method, the secondary crystal seeding method and the surface modification method were presented in detail. Furthermore, prospective avenues for future research and the associated challenges are briefly outlined.

Key words: continuous ZIF-8 membrane, hydrogen separation, in-situ growth method, secondary crystal seed method, carrier surface modification method

中图分类号:

谢钰麟, 饶瑞晔, 黄建, 蒿佳怡, 王友益, 黄琦. 连续ZIF-8膜制备及在氢气分离中的研究进展[J]. 化工进展, 2024, 43(S1): 403-418.

XIE Yulin, RAU Jui-yeh, HUANG Jian, HAO Jiayi, WANG Youyi, HUANG Qi. Preparation of continuous ZIF-8 membrane and its progress in hydrogen separation[J]. Chemical Industry and Engineering Progress, 2024, 43(S1): 403-418.

图/表 22

图1 沸石咪唑框架-8组成的三维结构[12]

图2 气体分离原理图[28]

图3 微米尺寸晶体膜以及纳米尺寸晶体膜的俯视图与横截面[20]

图4 在130℃下合成的沸石咪唑框架-8膜的电镜图[38]

图5 在氧化锌载体上原位生长合成沸石咪唑框架-8和沸石咪唑框架-9的示意图[42]

表1 原位生长法制备连续ZIF-8膜用于氢气分离的研究

年份	载体	测试条件	H₂渗透性/10^-7mol·Pa^-1·m^-2·s^-1	H₂/CO₂ （选择性）	H₂/N₂ （选择性）	H₂/CH₄ （选择性）	参考文献
2009	二氧化钛	25℃、0.1MPa	0.55	5.5	9.8	11.2	[36]
2014	多孔中空纤维陶瓷管	30℃、0.1MPa	19	4.9	12.9	15.6	[44]
2014	多孔聚矾	35℃、0.1MPa	2.2	—	12.4	10.5	[20]
2016	氮化硅中空纤维	25℃、0.2 MPa	1.15	11.67	—	—	[38]
2016	氧化铝载片	20℃、0.1MPa	6.4	10.0	13.2	16.7	[46]
2018	二维石墨氮化碳纳米片	25℃、0.1MPa	0.67	42	—	—	[45]
2023	氧化锌载片	25℃、0.1MPa	22.6	—	—	9.7	[42]

图6 在氧化铝载体上二次晶种法合成沸石咪唑框架-8示意图[49]

图7 聚醚砜/沸石咪唑框架-8复合膜的制备工艺[52]Ⅰ—用相转化技术制备聚醚砜中空纤维；Ⅱ—溶剂热法制备沸石咪唑框架-8膜

表2 二次晶种法制备连续ZIF-8膜用于氢气分离的研究

年份	载体	测试条件	H₂渗透性/10^-7mol·Pa^-1·m^-2·s^-1	H₂/CO₂ （选择性）	H₂/N₂ （选择性）	H₂/CH₄ （选择性）	参考文献
2012	聚醚砜	60℃、0.1MPa	4.0	—	9.9	10.7	[56]
2013	中空陶瓷纤维管	30℃、0.1MPa	11.0	5.2	7.3	6.8	[50]
2015	大孔氧化铝载片	25℃、0.1MPa	76.8	—	9.4	14.2	[57]
2016	氧化铝载片	25℃、0.1MPa	2.08	4.47	13.35	—	[51]
2019	聚醚砜	25℃、0.1MPa	112.8	7.78	5.48	3.38	[52]
2019	聚砜	25℃、0.1MPa	24.5	4.5	23.2	31.5	[53]
2020	氧化铝中空纤维	25℃、0.098MPa	5.5	—	30.9 ± 1.8	—	[55]
2022	氧化铝管	30℃、0.1MPa	6.1	—	—	12.4	[54]

图8 形成致密沸石咪唑框架-8膜的机理示意图[35]

图9 利用聚多巴胺作为偶联剂在氧化铝载片上合成沸石咪唑框架-8膜示意图[58]以及利用(3-氨基丙基)三乙氧基硅烷作为偶联剂在氧化铝载片上合成沸石咪唑框架-8膜示意图[60]

图10 利用固有微孔聚合物为界面层在二氧化硅载片上合成沸石咪唑框架-8膜示意图[61]

图11 在氧化铝表面通过氧气等离子体改性制备沸石咪唑框架-8和沸石咪唑框架-67膜的示意图[65]

图12 在氧化铝圆盘、二氧化钛圆盘、硅板和聚四氟乙烯圆盘上制备的沸石咪唑框架-8膜层的表面电镜图像以及对应载体的水接触角[66]

图13 用POTS改性后在疏水氧化铝载体上制备沸石咪唑框架-8膜的示意图[66]

表3 载体表面修饰法制备连续ZIF-8膜用于氢气分离的研究

年份	载体	测试条件	H₂渗透性/10^-7mol·Pa^-1·m^-2·s^-1	H₂/CO₂ （选择性）	H₂/N₂ （选择性）	H₂/CH₄ （选择性）	参考文献
2010	氧化铝载片	25℃、0.1MPa	约2.1	—	11.6	13	[35]
2012	大孔氧化铝载片	25℃、0.05MPa	573	17.05	15.44	—	[60]
2013	氧化铝载片	150℃、0.1MPa	1.8	8.9	16.2	31.5	[58]
2014	大孔不锈钢网	100℃、0.1MPa	211	8.1	15.0	23.2	[59]
2017	不锈钢网	100℃、0.1MPa	13.33	9.9	17.2	26.0	[72]
2018	氧化铝载片	200℃、0.1MPa	2.1	15.8	22.6	40.6	[66]
2021	氧化铝载片	25℃、0.1MPa	9.6	11.9	—	33.3	[61]
2021	聚合物中空纤维	25℃、0.1MPa	3.3	15.6	15.9	35.1	[73]
2022	氧化铝载片	150℃、0.1MPa	6.15	—	—	20.8	[74]
2022	二氧化硅载片	25℃、0.1MPa	19.05	11.9	—	—	[61]
2023	多孔氨基化聚醚砜中空纤维	150℃、0.1MPa	253.6	约21.2	—	—	[71]
2023	氧化铝载片	25℃、0.1MPa	1.86	8.72	—	31.03	[65]

图14 用液相外延生长法在氧化铝载体上制备沸石咪唑框架-8膜的示意图[76]

图15 用在各种基片上合成ZIF-8薄膜的电泳核组件法工艺示意图[77]

图16 利用无溶剂合成法在氧化铝载体上制备沸石咪唑框架-8膜的示意图[78]

图17 片状二锌四苯并咪唑膜的 ISIA 方法设计[79]（左图和中图为自制的不锈钢原位界面组装反应器；右图为用于二锌四苯并咪唑膜的原位界面组装工艺）

图18 MXene-沸石咪唑框架-8双层复合膜快速合成原理图[80]

图19 在多孔胺化聚醚砜中空纤维上制备沸石咪唑框架-8膜的工艺流程[71]

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连续ZIF-8膜制备及在氢气分离中的研究进展

Preparation of continuous ZIF-8 membrane and its progress in hydrogen separation

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