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

doi:10.6023/A25060242

Acta Chimica Sinica ›› 2026, Vol. 84 ›› Issue (1): 129-134.DOI: 10.6023/A25060242 Previous Articles Next Articles

Article

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)

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Abstract

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

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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.

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Fig. & Tab. 12

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

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

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

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

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

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

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

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

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

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

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

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

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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

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垂直排列金属有机框架纳米片膜实现高效H2传输