垂直排列金属有机框架纳米片膜实现高效H2传输

doi:10.6023/A25060242

化学学报 ›› 2026, Vol. 84 ›› Issue (1): 129-134.DOI: 10.6023/A25060242 上一篇下一篇

研究论文

垂直排列金属有机框架纳米片膜实现高效H₂传输

叶舣^a^,^†, 黄正义^b^,^†, 赵兴雷^a, 赵娅俐^b, 刘龙杰^a, 吴武凤^b^,^*(), 魏嫣莹^b^,^*()

^a 中国石油集团安全环保技术研究院有限公司石油石化污染物控制与处理国家重点实验室北京 102206
^b 华南理工大学化学与化工学院先进造纸与纸基材料全国重点实验室广东省绿色化工产品技术重点实验室广东广州 510640

投稿日期:2025-06-30 发布日期:2025-08-03
基金资助:
国家自然科学基金(U23A20115); 广东省自然科学基金(2024A1515012724); 广州市科技计划项目(2024A04J6251); 先进造纸与纸基材料全国重点实验室(2024ZD03); 石油石化污染物控制与处理国家重点实验室开放课题(PPC2023001); 中国石油集团科研项目(RISE2023KY13)

Vertically Aligned Metal-organic Framework Nanosheet Membranes for Efficient H₂ Transport

Yi Ye^a, Zhengyi Huang^b, Xinglei Zhao^a, Yali Zhao^b, Longjie Liu^a, Wufeng Wu^b^,^*(), Yanying Wei^b^,^*()

^a State Key Laboratory of Petroleum Pollution Control, CNPC Research Institute of Safety and Environmental Technology, Beijing 102206, China
^b State Key Laboratory of Pulp and Paper Engineering, School of Chemistry and Chemical Engineering, Guangdong Provincial Key Lab of Green Chemical Product Technology, South China University of Technology, Guangzhou 510640, China

Received:2025-06-30 Published:2025-08-03
Contact: * E-mail: wuwufeng@scut.edu.cn;ceyywei@scut.edu.cn
About author:
† These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(U23A20115); Natural Science Foundation of Guangdong Province(2024A1515012724); Guangzhou Municipal Science and Technology Project(2024A04J6251); State Key Laboratory of Pulp and Paper Engineering(2024ZD03); Open Project Program of State Key Laboratory of Petroleum Pollution Control(PPC2023001); Scientific Research Project of China National Petroleum Corporation(RISE2023KY13)

文章分享

1. Supporting Information129-A25060242.pdf(636KB)

摘要/Abstract

当前全球90%以上的氢气生产依赖于天然气重整工艺, 因此实现高效的碳脱除及氢气提纯对推动高纯度氢能的大规模应用具有重要意义. 具有有序多孔结构的金属有机框架(MOFs)纳米片膜在氢气纯化领域展现出巨大潜力. 然而, MOF纳米片膜面临传统水平堆叠方式所带来的气体传输路径迂回问题, 严重制约了其传质效率. 为此, 本研究采用一种快速电流驱动策略, 在短短10 min内实现了垂直MOF纳米片膜的原位构筑. 该垂直排列结构显著改善了气体分子的扩散路径, 所制备的垂直MOF纳米片膜表现出了极高的H₂渗透性能, 其渗透率达到1.5×10^-6 mol•m^-2•s^-1•Pa^-1, 相较于传统的水平堆叠结构膜提升了5倍. 同时, 在H₂/CO₂体系中仍保持了良好的分离选择性(选择性约为20). 该研究为二维MOF材料的垂直构筑与高性能分离应用提供了新的理论基础与技术路径.

关键词: 膜分离, 气体分离, 金属有机框架(MOF)膜

Over 90% of global hydrogen (H₂) production is derived from natural gas reforming, making efficient carbon removal and H₂ purification crucial for high-purity hydrogen applications. Metal-organic framework (MOF) nanosheet membranes, with highly ordered porous structures, show great potential for H₂ purification. Gas transport in conventional MOF nanosheet membranes is constrained by horizontal stacking, which severely limits gas mass transfer efficiency. Here we propose a fast current-driven synthesis strategy for in situ fabrication of vertically aligned MOF nanosheet membranes within a short duration of 10 min. The electric field assistance effectively induces linker deprotonation, thereby accelerating the nucleation and preferential growth of MOF nanosheets on the substrate. As the reaction progresses, the increasing spatial constraints hinder crystal lateral growth, compelling the crystal growth to preferentially proceed along the direction of minimal resistance. In other words, the growth orientation gradually transitions from an initially parallel arrangement to a vertically aligned structure. Compared with conventional horizontally stacked structure, the vertically aligned structure significantly shortens the gas diffusion pathways, effectively eliminating mass transfer limitations caused by horizontal stacking. The resulting vertically aligned copper 1,4-benzenedicarboxylate (CuBDC) nanosheet membrane exhibits outstanding H₂ permeance of 1.5×10^-6 mol•m^-2•s^-1•Pa^-1, approximately 5 times higher than that of conventional nanosheet membranes with horizontally stacked structure. Meanwhile, the vertically aligned CuBDC nanosheet membrane maintains excellent selectivity in H₂/CO₂ separation, with a selectivity of ca. 20, driven by both adsorption and diffusion. Due to both the higher diffusion resistance of larger gas molecules and the strong interactions between metal sites and CO₂ molecules, CO₂ transport within the membrane is significantly hindered, while H₂ molecules permeate more readily, ultimately resulting in enhanced H₂/CO₂ separation performance. This work not only confirms the critical role of vertically aligned structures in improving molecular transport efficiency but also provides new theoretical insight and a practical strategy for fabricating vertically aligned 2D MOF membranes for efficient gas separation.

Key words: membrane separation, gas separation, metal-organic framework (MOF) membrane

引用此文

叶舣, 黄正义, 赵兴雷, 赵娅俐, 刘龙杰, 吴武凤, 魏嫣莹. 垂直排列金属有机框架纳米片膜实现高效H₂传输[J]. 化学学报, 2026, 84(1): 129-134.

Yi Ye, Zhengyi Huang, Xinglei Zhao, Yali Zhao, Longjie Liu, Wufeng Wu, Yanying Wei. Vertically Aligned Metal-organic Framework Nanosheet Membranes for Efficient H₂ Transport[J]. Acta Chimica Sinica, 2026, 84(1): 129-134.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 12

图1. 垂直CuBDC纳米片膜制备过程示意图

Figure 1. Schematic illustration of the vertical CuBDC nanosheet membrane fabrication process

图2. (a)涂敷Pt层的AAO基底和(b) CuBDC纳米片膜的照片

Figure 2. Photographs of (a) AAO substrate coated with Pt layer and (b) CuBDC nanosheet membrane

图3. (a)涂覆Pt层的AAO基底与(b~f)基于不同反应时间制备的CuBDC纳米片膜的表面SEM图像

Figure 3. Top-view SEM images of (a) AAO substrate coated with Pt layer and (b~f) CuBDC nanosheet membranes prepared at different reaction times

图4. 反应10 min制备的CuBDC纳米片膜横截面SEM图像

Figure 4. SEM cross-sectional view of the CuBDC nanosheet membrane prepared after 10 min

图5. (a)基于不同反应时间制备的CuBDC纳米片膜的XRD图谱; CuBDC晶体沿[001]方向的(b)侧视图与(c)俯视图

Figure 5. (a) XRD patterns of the CuBDC nanosheet membranes prepared at different reaction times. (b) Side and (c) top views of CuBDC crystal along the [001] direction

图6. 反应10 min制备的CuBDC纳米片膜表面SEM图及对应的EDS图像

Figure 6. Top-view SEM image and corresponding EDS mapping of the CuBDC nanosheet membrane prepared after 10 min

图7. 反应10 min制备的CuBDC纳米片膜的FTIR光谱图

Figure 7. FTIR spectrum of the CuBDC nanosheet membrane prepared after 10 min

图8. 基于不同反应时间制备的CuBDC纳米片膜的气体分离性能

Figure 8. Gas separation performance of CuBDC nanosheet membranes prepared under varying reaction times

图9. 反应10 min制备的CuBDC纳米片膜的单气体渗透性能

Figure 9. Single-gas permeation performance of CuBDC nanosheet membrane prepared after 10 min reaction

图10. (a) CuBDC纳米片的SEM图像; (b)水平堆叠CuBDC纳米片膜的横截面SEM图像

Figure 10. (a) SEM image of CuBDC nanosheet; (b) SEM cross-sectional view of horizontally stacked CuBDC nanosheet membrane

图11. (a)模拟的体相CuBDC、传统方法制备的CuBDC纳米片及相应的水平堆叠膜的XRD图谱对比; (b) CuBDC晶体沿$[\bar{2}01] $方向的俯视图

Figure 11. (a) Comparison of XRD patterns of simulated bulk CuBDC, CuBDC nanosheets synthesized via the conventional method, and the corresponding horizontally stacked membrane; (b) top view of CuBDC crystal along the $[\bar{2}01] $ direction

图12. 水平膜和垂直膜的气体分离性能对比

Figure 12. Comparison of gas separation performance between the horizontally stacked membrane and the vertically aligned membrane

参考文献 32

[1]	Gunathilake, C.; Soliman, I.; Panthi, D.; Tandler, P.; Fatani, O.; Alias Ghulamullah, N.; Marasinghe, D.; Farhath, M.; Madhujith, T.; Conrad, K.; Du, Y.; Jaroniec, M. Chem. Soc. Rev. 2024, 53, 10900. doi: 10.1039/D3CS00731F
[2]	Bhuiyan, M. M. H.; Siddique, Z. I. Int. J. Hydrogen Energy 2025, 102, 1026. doi: 10.1016/j.ijhydene.2025.01.033
[3]	Acar, C.; Dincer, I. Int. J. Hydrogen Energy 2020, 45, 3396. doi: 10.1016/j.ijhydene.2018.10.149
[4]	Wei, S.; Sacchi, R.; Tukker, A.; Suh, S.; Steubing, B. Energy Environ. Sci. 2024, 17, 2157. doi: 10.1039/D3EE03875K
[5]	Yang, L.; Qian, S.; Wang, X.; Cui, X.; Chen, B.; Xing, H. Chem. Soc. Rev. 2020, 49, 5359. doi: 10.1039/C9CS00756C
[6]	Sholl, D. S.; Lively, R. P. Nature 2016, 532, 435. doi: 10.1038/532435a
[7]	Zhang, M.; Zhang, Y.; Qin, J.; Feng, X.; Li, X.; Chang, T.; Yang, H. Acta Chim. Sinica 2025, 83, 132. (in Chinese) doi: 10.6023/A24120388
	(张蒙茜, 张玉莹, 秦家轩, 冯霄, 李雪艳, 畅通, 杨海英, 化学学报, 2025, 83, 132.) doi: 10.6023/A24120388
[8]	Lyu, L.; Zhao, Y.; Wei, Y.; Wang, H. Acta Chim. Sinica 2021, 79, 869. (in Chinese) doi: 10.6023/A21030099
	(吕露茜, 赵娅俐, 魏嫣莹, 王海辉, 化学学报, 2021, 79, 869.) doi: 10.6023/A21030099
[9]	Gin, D. L.; Noble, R. D. Science 2011, 332, 674. doi: 10.1126/science.1203771
[10]	Park, H. B.; Kamcev, J.; Robeson, L. M.; Elimelech, M.; Freeman, B. D. Science 2017, 356, eaab0530. doi: 10.1126/science.aab0530
[11]	He, W.; Wang, B.; Feng, H.; Kong, X.; Li, T.; Xiao, R. Acta Chim. Sinica 2024, 82, 226. (in Chinese) doi: 10.6023/A23100467
	(何文, 王波, 冯晗俊, 孔祥如, 李桃, 肖睿, 化学学报, 2024, 82, 226.) doi: 10.6023/A23100467
[12]	Peng, Y.; Li, Y.; Ban, Y.; Jin, H.; Jiao, W.; Liu, X.; Yang, W. Science 2014, 346, 1356. doi: 10.1126/science.1254227
[13]	Wu, W.; Cai, X.; Yang, X.; Wei, Y.; Ding, L.; Li, L.; Wang, H. Nat. Commun. 2024, 15, 10730. doi: 10.1038/s41467-024-54663-7
[14]	Wang, X.; Chi, C.; Zhang, K.; Qian, Y.; Gupta, K. M.; Kang, Z.; Jiang, J.; Zhao, D. Nat. Commun. 2017, 8, 14460. doi: 10.1038/ncomms14460
[15]	Song. H.; Peng, Y.; Wang, C.; Shu, L.; Zhu, C.; Wang, Y.; He, H.; Yang, W. Angew. Chem. Int. Ed. 2023, 62, e202218472.
[16]	Xu, L.; Li, S.; Mao, H.; Li, Y.; Zhang, A.; Wang, S.; Liu, W.; Lv, J.; Wang, T.; Cai, W.; Sang, L.; Xie, W.; Pei, C.; Li, Z.; Feng, Y.; Zhao. Z. Science 2022, 378, 308. doi: 10.1126/science.abo5680 pmid: 36264816
[17]	Adams, R.; Carson, C.; Ward, J.; Tannenbaum, R.; Koros, W. Micropor. Mesopor. Mater. 2010, 131, 13. doi: 10.1016/j.micromeso.2009.11.035
[18]	Rodenas, T.; Luz, I.; Prieto, G.; Seoane, B.; Miro, H.; Corma, A.; Kapteijn, F.; Llabrés i Xamena, F. X.; Gascon, J. Nat. Mater. 2015, 14, 48. doi: 10.1038/nmat4113 pmid: 25362353
[19]	Kallo, M. T.; Lennox, M. J. Langmuir 2020, 36, 13591. doi: 10.1021/acs.langmuir.0c02434
[20]	Carson, C. G.; Brunnello, G.; Lee, S.; Jang, S.; Gerhardt, R. A.; Tannenbaum, R. Eur. J. Inorg. Chem. 2014, 2140.
[21]	Zhou, S.; Wei, Y.; Li, L.; Duan, Y.; Hou, Q.; Zhang, L.; Ding, L.; Xue, J.; Wang, H.; Caro, J. Sci. Adv. 2018, 4, eaau1393. doi: 10.1126/sciadv.aau1393
[22]	Hou, Q.; Zhou, S.; Wei, Y.; Caro, J.; Wang, H. J. Am. Chem. Soc. 2020, 142, 9582.
[23]	He, M.; Zhang, Y.; Wang, Y.; Wang, X.; Li, Y.; Hu, Na.; Wu, T.; Zhang, F.; Dai, Z.; Chen, X.; Kita, H. Sep. Purif. Technol. 2021, 275, 119109. doi: 10.1016/j.seppur.2021.119109
[24]	Li, Y.; Bux, H.; Feldhoff, A.; Li, G.; Yang, W.; Caro, J. Adv. Mater. 2010, 22, 3322. doi: 10.1002/adma.201000857
[25]	Sun, Y.; Liu, Y.; Caro, J.; Guo, X.; Song, C.; Liu, Y. Angew. Chem. Int. Ed. 2018, 57, 16088. doi: 10.1002/anie.v57.49
[26]	Yang, F.; Wu, M.; Wang, Y.; Ashtiani, S.; Jiang, H. ACS Appl. Mater. Interfaces 2019, 11, 990. doi: 10.1021/acsami.8b19480
[27]	Zhou, X.; Dong, J.; Zhu, Y.; Liu, L.; Jiao, Yan.; Li, H.; Han, Y.; Davey, K.; Xu, Q.; Zheng, Y.; Qiao, S. J. Am. Chem. Soc. 2021, 143, 6681. doi: 10.1021/jacs.1c02379
[28]	Zhan, G.; Fan, L.; Zhao, F.; Huang, Z.; Chen, B.; Yang, X.; Zhou, S. Adv. Funct. Mater. 2019, 29, 1806720. doi: 10.1002/adfm.v29.9
[29]	Zhang, F.; Zhang, J.; Zhang, B.; Zheng, L.; Cheng, X.; Wan, Q.; Han, B.; Zhang, J. Nat. Commun. 2020, 11, 1431. doi: 10.1038/s41467-020-15200-4
[30]	Chang, M.; Wang, F.; Wei, Y.; Yang, Q.; Wang, J.; Liu, D.; Chen, J. AIChE J. 2022, 68, e17794. doi: 10.1002/aic.v68.9
[31]	Fu, Y.; Yao, Y.; Forse, A. C.; Li, J.; Mochizuki, K.; Long, J. R.; Reimer, J. A.; De Paëpe, G.; Kong, X.; Nat. Commun. 2023, 14, 2386. doi: 10.1038/s41467-023-38155-8 pmid: 37185270
[32]	Zhang, F.; Shang, H.; Zhai, B., Li, X.; Zhang, Y.; Wang, X.; Li, J.; Yang, J. AIChE J. 2023, 69, e18079. doi: 10.1002/aic.v69.6

垂直排列金属有机框架纳米片膜实现高效H₂传输

Vertically Aligned Metal-organic Framework Nanosheet Membranes for Efficient H₂ Transport

RichHTML

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 12

参考文献 32

相关文章 11

编辑推荐

相关统计

本文评价

[1]	何文, 王波, 冯晗俊, 孔祥如, 李桃, 肖睿. CO₂捕集膜分离的Pebax基材料研究进展[J]. 化学学报, 2024, 82(2): 226-241.
[2]	曾少娟, 孙雪琦, 白银鸽, 白璐, 郑爽, 张香平, 张锁江. CO₂捕集分离的功能离子液体及材料研究进展^★[J]. 化学学报, 2023, 81(6): 627-645.
[3]	李崇, 李娜, 常立美, 谷志刚, 张健. 金属-有机框架HKUST-1膜在气体分离中研究进展^※[J]. 化学学报, 2022, 80(3): 340-358.
[4]	吕露茜, 赵娅俐, 魏嫣莹, 王海辉. 二维金属-有机骨架膜的制备及其在分离中的应用[J]. 化学学报, 2021, 79(7): 869-884.
[5]	付静茹, 贲腾. 一种新型的共价有机骨架膜的制备与气体分离性能[J]. 化学学报, 2020, 78(8): 805-814.
[6]	蒋成浩, 冯霄, 王博. 共价有机框架膜的制备及其在海水淡化和水处理领域的研究进展[J]. 化学学报, 2020, 78(6): 466-477.
[7]	蔡铖智, 李丽凤, 邓小梅, 李树华, 梁红, 乔智威. 基于机器学习和高通量计算筛选金属有机框架的甲烷/乙烷/丙烷分离性能[J]. 化学学报, 2020, 78(5): 427-436.
[8]	刘蓓, 唐李兴, 廉源会, 李智, 孙长宇, 陈光进. 互穿结构及混合配体对金属-有机骨架材料分离性能的影响[J]. 化学学报, 2013, 71(06): 920-928.
[9]	付升, 于养信, 王晓琳. 纳滤膜对电解质溶液分离特性的理论研究(II): 混合电解质溶液[J]. 化学学报, 2007, 65(10): 923-929.
[10]	付升, 于养信, 高光华, 王晓琳. 纳滤膜对电解质溶液分离特性的理论研究(I): 单一电解质溶液[J]. 化学学报, 2006, 64(22): 2241-2246.
[11]	程志林,晁自胜,方维平,林海强,方惠霖. 添加成膜促进剂合成致密ZSM-5分子筛膜[J]. 化学学报, 2003, 61(12): 1944-1948.