共价有机框架膜在乙醇和水分离应用的研究进展
Advances in Covalent Organic Framework Membranes for Ethanol-Water Separation
DOI: 10.12677/aac.2026.161004, PDF,   
作者: 冯 悦, 李 丹, 周 丹, 杨茂春：浙江师范大学含氟新材料研究所先进催化材料教育部重点实验室，浙江 金华
关键词: 晶态多孔有机材料；共价有机框架；渗透汽化膜；乙醇除水；Crystalline Porous Organic Materials； Covalent Organic Frameworks； Pervaporation Membranes； Ethanol Dehydration
摘要: 生物燃料乙醇的绿色生产是缓解能源危机与环境污染的关键策略之一，而高效的乙醇提纯技术是其产业化核心。渗透汽化膜分离技术因其能耗低、效率高、操作简单等优点，被视为极具前景的提纯方案。共价有机框架作为一种由共价键连接而成的、具有永久孔隙率和高度有序结构的新型结晶多孔材料，其精准可调的孔径与丰富的理化性质，为构筑高性能的渗透汽化膜材料提供了广阔的前景。本文系统阐述了近年来COF膜材料在乙醇脱水领域的研究进展。首先概述了渗透汽化除水的基本原理及对膜材料的关键要求，其次阐述了COF膜的三种主要构筑策略，探讨了当前COF膜在规模化制备、结构稳定性及实际工况耐受性等方面面临的挑战，并对未来研究方向进行了展望，希望为开发高效乙醇–水分离的渗透汽化膜材料提供参考。
Abstract: The green production of biofuel ethanol is recognized as a pivotal strategy for alleviating the energy crisis and mitigating environmental pollution, with efficient ethanol purification serving as the core of its industrialization. Owing to the advantages of low energy consumption, high efficiency, and operational simplicity, pervaporation membrane separation technology is regarded as a highly promising purification solution. As a novel class of crystalline porous materials connected by covalent bonds, Covalent Organic Frameworks (COFs) possess permanent porosity and highly ordered structures. Their precisely tunable pore sizes and rich physicochemical properties offer broad prospects for constructing high-performance pervaporation membrane materials. This paper systematically reviews the recent research progress in COF membranes for ethanol dehydration. First, the fundamental principles of pervaporation dehydration and the critical requirements for membrane materials are outlined. Subsequently, three primary construction strategies for COF membranes are elaborated. Furthermore, the current challenges faced by COF membranes regarding large-scale fabrication, structural stability, and tolerance to practical operating conditions are discussed. Finally, future research directions are highlighted, aiming to provide a reference for the development of high-efficiency pervaporation membrane materials for ethanol-water separation.
文章引用：冯悦, 李丹, 周丹, 杨茂春. 共价有机框架膜在乙醇和水分离应用的研究进展[J]. 分析化学进展, 2026, 16(1): 29-35. https://doi.org/10.12677/aac.2026.161004

参考文献

[1] Zabed, H., Sahu, J.N., Boyce, A.N. and Faruq, G. (2016) Fuel Ethanol Production from Lignocellulosic Biomass: An Overview on Feedstocks and Technological Approaches. Renewable and Sustainable Energy Reviews, 66, 751-774. [Google Scholar] [CrossRef] 
[2] Huber, G.W., Iborra, S. and Corma, A. (2006) Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering. Chemical Reviews, 106, 4044-4098. [Google Scholar] [CrossRef] [PubMed]
[3] Vane, L.M. (2005) A Review of Pervaporation for Product Recovery from Biomass Fermentation Processes. Journal of Chemical Technology & Biotechnology, 80, 603-629. [Google Scholar] [CrossRef] 
[4] Kiss, A.A. and Suszwalak, D.J.P.C. (2012) Enhanced Bioethanol Dehydration by Extractive and Azeotropic Distillation in Dividing-Wall Columns. Separation and Purification Technology, 86, 70-78. [Google Scholar] [CrossRef] 
[5] Chapman, P.D., Oliveira, T., Livingston, A.G. and Li, K. (2008) Membranes for the Dehydration of Solvents by Pervaporation. Journal of Membrane Science, 318, 5-37. [Google Scholar] [CrossRef] 
[6] Shao, P. and Huang, R.Y.M. (2007) Polymeric Membrane Pervaporation. Journal of Membrane Science, 287, 162-179. [Google Scholar] [CrossRef] 
[7] Peng, P., Lan, Y., Liang, L. and Jia, K. (2021) Membranes for Bioethanol Production by Pervaporation. Biotechnology for Biofuels, 14, Article No. 10. [Google Scholar] [CrossRef] [PubMed]
[8] Park, H.B., Kamcev, J., Robeson, L.M., Elimelech, M. and Freeman, B.D. (2017) Maximizing the Right Stuff: The Trade-Off between Membrane Permeability and Selectivity. Science, 356, eaab0530. [Google Scholar] [CrossRef] [PubMed]
[9] Côté, A.P., Benin, A.I., Ockwig, N.W., O’Keeffe, M., Matzger, A.J. and Yaghi, O.M. (2005) Porous, Crystalline, Covalent Organic Frameworks. Science, 310, 1166-1170. [Google Scholar] [CrossRef] [PubMed]
[10] Geng, K., He, T., Liu, R., Dalapati, S., Tan, K.T., Li, Z., et al. (2020) Covalent Organic Frameworks: Design, Synthesis, and Functions. Chemical Reviews, 120, 8814-8933. [Google Scholar] [CrossRef] [PubMed]
[11] SMITHA, B. (2004) Separation of Organic? Organic Mixtures by Pervaporation? A Review. Journal of Membrane Science, 241, 1-21. [Google Scholar] [CrossRef] 
[12] Wang, Z., Zhang, S., Chen, Y., Zhang, Z. and Ma, S. (2020) Covalent Organic Frameworks for Separation Applications. Chemical Society Reviews, 49, 708-735. [Google Scholar] [CrossRef] [PubMed]
[13] Dey, K., Pal, M., Rout, K.C., Kunjattu H, S., Das, A., Mukherjee, R., et al. (2017) Selective Molecular Separation by Interfacially Crystallized Covalent Organic Framework Thin Films. Journal of the American Chemical Society, 139, 13083-13091. [Google Scholar] [CrossRef] [PubMed]
[14] Wang, C., Tang, J., Li, L., Wan, J., Ma, Y., Jin, Y., et al. (2022) Ultrathin Self‐Standing Covalent Organic Frameworks toward Highly‐Efficient Nanofluidic Osmotic Energy Generator. Advanced Functional Materials, 32, Article ID: 2204068. [Google Scholar] [CrossRef] 
[15] Dechnik, J., Gascon, J., Doonan, C.J., Janiak, C. and Sumby, C.J. (2017) Mixed‐Matrix Membranes. Angewandte Chemie International Edition, 56, 9292-9310. [Google Scholar] [CrossRef] [PubMed]
[16] Wang, C., Li, Z., Chen, J., et al. (2019) Covalent Organic Framework-Based Mixed Matrix Membranes for Pervaporation Dehydration of Ethanol. AIChE Journal, 65, e16624.
[17] Liu, G,. Jiang, Z., Yang, H., et al. (2020) Enhanced Performance of Mixed Matrix Membrane by Incorporating a Covalent Organic Framework for Ethanol Dehydration. Separation and Purification Technology, 234, Article ID: 116110.
[18] Zhu, J., Hou, J., Zhang, R., et al. (2020) High-Performance Mixed Matrix Membranes for Ethanol Dehydration by Incorporating Amine-Functionalized Covalent Organic Frameworks. Journal of Materials Chemistry A, 8, 5202-5211.
[19] Cheng, Y., Wang, X., Jia, C., et al. (2021) Ultrathin Mixed Matrix Membranes Containing Two-Dimensional Covalent Organic Framework Nanosheets for Efficient Pervaporation Dehydration. Journal of Membrane Science, 618, Article ID: 118697.
[20] Fan, H., Peng, M., Strauss, I., et al. (2019) Large-Area, Free-Standing, Two-Dimensional Covalent Organic Framework Thin Films for Highly Efficient Molecular Separation. Advanced Materials, 31, Article ID: 1904948.
[21] Zhao, S., Wang, Z., Zhang, J., et al. (2020) Layer-By-Layer Assembly of Covalent Organic Framework Nanosheets and Graphene Oxide for Molecular Sieving Membranes. ACS Applied Nano Materials, 3, 5529-5537.
[22] Li, X., Wang, H., Zhang, F., et al. (2021) Covalent Organic Framework Membranes Grafted on a Porous Substrate for High-Flux Nanofiltration. Angewandte Chemie International Edition, 60, 11253-11257.
[23] Peng, Y., Huang, Y., Zhu, Y., et al. (2017) Ultrathin Two-Dimensional Covalent Organic Framework Nanosheets: Preparation and Application in Highly Selective and Stable Pervaporation. Chemical Communications, 53, 10006-10009.
[24] Kuhn, P., Antonietti, M. and Thomas, A. (2008) Porous, Covalent Triazine‐Based Frameworks Prepared by Ionothermal Synthesis. Angewandte Chemie International Edition, 47, 3450-3453. [Google Scholar] [CrossRef] [PubMed]
[25] Kang, Z., Peng, Y., Qian, Y., et al. (2018) Mixed Matrix Membranes with Molecular-Interaction-Driven Tunable Free Volumes for Efficient Bio-Fuel Recovery. Journal of Materials Chemistry A, 6, 8725-8733.
[26] Qian, H.L., Yang, C.X. and Yan, X.P. (2020) Ionothermal Synthesis of a Crystalline Covalent Organic Framework for Molecular Sieving. ACS Nano, 14, 13333-13341.
[27] Li, Y., He, G., Wang, S., et al. (2022) Sulfonated Covalent Organic Framework Based Mixed Matrix Membranes for Highly Efficient Dehydration of Ethanol. Chemical Engineering Journal, 428, Article ID: 131028.
[28] Sheng, F., Wu, B., Li, X., et al. (2021) Zwitterionic Covalent Organic Frameworks: Attractive Porous Materials for Water-Related Applications. Advanced Functional Materials, 31, Article ID: 2103471.
[29] Li, G., Wang, Z., Zheng, S., et al. (2022) Covalent Organic Framework-Based Heterostructured Membranes for Precise Molecular Sieving. Nature Communications, 13, Article No. 3160.
[30] Zhang, W., Li, P., Wang, H., et al. (2023) Gradient Distributed COF Fillers in Mixed Matrix Membranes for Enhanced Ethanol Dehydration. Journal of Membrane Science, 668, Article ID: 121245.
[31] Jiang, D., Chen, M., Wang, H., et al. (2022) Green Synthesis of Covalent Organic Frameworks: Prospects and Challenges. Chemical Communications, 58, 786-798.
[32] Evans, A.M., Parent, L.R., Flanders, N.C., et al. (2018) Water-Stable, Hydroxamate-Based, Porous, and Crystalline Covalent Organic Frameworks. Angewandte Chemie International Edition, 57, 137-142.

为你推荐