Liquid-phase Exfoliation of Pyridine-based Covalent Organic Framework Nanosheets for High-performance H<sub>2</sub>/CO<sub>2</sub> Gas Separation Membrane Fabrication

Hong-yu Zuo; Wei-yi Zhang; Yao-zu Liao

doi:10.11777/j.issn1000-3304.2025.25003

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Liquid-phase Exfoliation of Pyridine-based Covalent Organic Framework Nanosheets for High-performance H₂/CO₂ Gas Separation Membrane Fabrication

更新时间：2025-04-28

- Liquid-phase Exfoliation of Pyridine-based Covalent Organic Framework Nanosheets for High-performance H₂/CO₂ Gas Separation Membrane Fabrication
- Acta Polymerica Sinica Pages: 1-11(2025)
- 作者机构：
  
  东华大学材料科学与工程学院纤维材料改性国家重点实验室上海 201620
- 作者简介：
  
  Wei-yi Zhang, E-mail: wyzhang@dhu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25003
  CLC：
- CSTR：32057.14.GFZXB.2025.7369
- Received：02 January 2025，
  
  Accepted：2025-02-24，
  
  Published Online：28 April 2025，
- 稿件说明：
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左宏瑜, 张卫懿, 廖耀祖. 液相剥离吡啶基共价有机框架纳米片组装成膜用于高效H₂/CO₂气体分离. 高分子学报, doi: 10.11777/j.issn1000-3304.2025.25003

Zuo, H. Y.; Zhang, W. Y.; Liao, Y. Z. Liquid-phase exfoliation of pyridine-based covalent organic framework nanosheets for high-performance H₂/CO₂ gas separation membrane fabrication. Acta Polymerica Sinica, doi: 10.11777/j.issn1000-3304.2025.25003
左宏瑜, 张卫懿, 廖耀祖. 液相剥离吡啶基共价有机框架纳米片组装成膜用于高效H₂/CO₂气体分离. 高分子学报, doi: 10.11777/j.issn1000-3304.2025.25003 DOI： CSTR： 32057.14.GFZXB.2025.7369.

Zuo, H. Y.; Zhang, W. Y.; Liao, Y. Z. Liquid-phase exfoliation of pyridine-based covalent organic framework nanosheets for high-performance H₂/CO₂ gas separation membrane fabrication. Acta Polymerica Sinica, doi: 10.11777/j.issn1000-3304.2025.25003 DOI： CSTR： 32057.14.GFZXB.2025.7369.

摘要

共价有机框架纳米片(CONs)是一种具有优异性质的二维片层材料，共价有机框架(COF)材料所具有的可预设计的周期性结构、原子级精度、定制功能性、良好的热稳定性、永久性孔隙以及极低的密度等特性更是赋予了CONs更大的开发潜力. 针对COF纳米片剥离效率低、尺寸可控性差导致膜制备工艺复杂的问题，采用液相剥离法制备吡啶基COF纳米片(TpBpy-CON)并组装成COF膜(TpBpy-COM). 在温和条件下对COF粉末进行剥离，获得均匀分散的TpBpy-CON. 由此方法制得的COF纳米片具有较高的纵横比、比表面积及孔隙率. 进而，通过真空辅助技术将纳米片组装成COF膜. 所制备的TpBpy-COM膜展现出致密的表面结构和优异的H

/CO

气体分离性能.

Abstract

Covalent organic framework nanosheets (CONs) are a class of two-dimensional layered materials with exceptional properties. The inherent features of COF materials

such as pre-designable periodic structures

atomic-level precision

tunable functionality

excellent thermal stability

permanent porosity

and ultralow density

endow CONs with significant potential for further development. However

challenges such as low exfoliation efficiency of COF nanosheets and poor size controllability complicate membrane fabrication processes. In this st

udy

a liquid-phase exfoliation method was employed to prepare pyridine-based COF nanosheets (TpBpy-CON) and assemble them into COF membranes (TpBpy-COM). COF powders were exfoliated under mild conditions to obtain size-controllable TpBpy-CON. The resulting COF nanosheets exhibited high aspect ratios

specific surface areas

and porosity. Subsequently

the nanosheets were assembled into COF membranes using vacuum-assisted techniques. The fabricated TpBpy-COM demonstrated a compact membrane surface structure and excellent H

/CO

gas separation performance.

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references

Qian Q. H. ; Asinger P. A. ; Lee M. J. ; Han G. ; Mizrahi Rodriguez K. ; Lin S. ; Benedetti F. M. ; Wu A. X. ; Chi W. S. ; Smith Z. P. MOF-based membranes for gas separations . Chem. Rev. , 2020 , 120 ( 16 ), 8161 - 8266 . doi: 10.1021/acs.chemrev.0c00119 http://dx.doi.org/10.1021/acs.chemrev.0c00119

Dechnik J. ; Gascon J. ; Doonan C. J. ; Janiak C. ; Sumby C. J. Mixed-matrix membranes . Angew. Chem. Int. Ed. , 2017 , 56 ( 32 ), 9292 - 9310 . doi: 10.1002/anie.201701109 http://dx.doi.org/10.1002/anie.201701109

Li X. S. ; Zhu Y. W. ; Cai W. W. ; Borysiak M. ; Han B. Y. ; Chen D. ; Piner R. D. ; Colombo L. ; Ruoff R. S. Transfer of large-area graphene films for high-performance transparent conductive electrodes . Nano Lett. , 2009 , 9 ( 12 ), 4359 - 4363 . doi: 10.1021/nl902623y http://dx.doi.org/10.1021/nl902623y

Li H. ; Song Z. N. ; Zhang X. J. ; Huang Y. ; Li S. G. ; Mao Y. T. ; Ploehn H. J. ; Bao Y. ; Yu M. Ultrathin, molecular-sieving graphene oxide membranes for selective hydrogen separation . Science , 2013 , 342 ( 6154 ), 95 - 98 . doi: 10.1126/science.1236686 http://dx.doi.org/10.1126/science.1236686

Peng Y. ; Li Y. S. ; Ban Y. J. ; Jin H. ; Jiao W. M. ; Liu X. L. ; Yang W. S. Membranes . Metal-organic framework nanosheets as building blocks for molecular sieving membranes. Science , 2014 , 346 ( 6215 ), 1356 - 1359 . doi: 10.1126/science.1254227 http://dx.doi.org/10.1126/science.1254227

Dakhchoune M. ; Villalobos L. F. ; Semino R. ; Liu L. M. ; Rezaei M. ; Schouwink P. ; Avalos C. E. ; Baade P. ; Wood V. ; Han Y. ; Ceriotti M. ; Agrawal K. V. Gas-sieving zeolitic membranes fabricated by condensation of precursor nanosheets . Nat. Mater. , 2021 , 20 ( 3 ), 362 - 369 . doi: 10.1038/s41563-020-00822-2 http://dx.doi.org/10.1038/s41563-020-00822-2

Zhang H. ; Xiao Q. ; Guo X. H. ; Li N. J. ; Kumar P. ; Rangnekar N. ; Jeon M. Y. ; Al-Thabaiti S. ; Narasimharao K. ; Basahel S. N. ; Topuz B. ; Onorato F. J. ; Macosko C. W. ; Mkhoyan K. A. ; Tsapatsis M. Open-pore two-dimensional MFI zeolite nanosheets for the fabrication of hydrocarbon-isomer-selective membranes on porous polymer supports . Angew. Chem. Int. Ed. , 2016 , 55 ( 25 ), 7184 - 7187 . doi: 10.1002/anie.201601135 http://dx.doi.org/10.1002/anie.201601135

Ma T. Q. ; Kapustin E. A. ; Yin S. X. ; Liang L. ; Zhou Z. Y. ; Niu J. ; Li L. H. ; Wang Y. Y. ; Su J. ; Li J. ; Wang X. G. ; Wang W. D. ; Wang W. ; Sun J. L. ; Yaghi O. M. Single-crystal X-ray diffraction structures of covalent organic frameworks . Science , 2018 , 361 ( 6397 ), 48 - 52 . doi: 10.1126/science.aat7679 http://dx.doi.org/10.1126/science.aat7679

Evans A. M. ; Parent L. R. ; Flanders N. C. ; Bisbey R. P. ; Vitaku E. ; Kirschner M. S. ; Schaller R. D. ; Chen L. X. ; Gianneschi N. C. ; Dichtel W. R. Seeded growth of single-crystal two-dimensional covalent organic frameworks . Science , 2018 , 361 ( 6397 ), 52 - 57 . doi: 10.1126/science.aar7883 http://dx.doi.org/10.1126/science.aar7883

Yaghi O. M. Reticular chemistry in all dimensions . ACS Cent. Sci. , 2019 , 5 ( 8 ), 1295 - 1300 . doi: 10.1021/acscentsci.9b00750 http://dx.doi.org/10.1021/acscentsci.9b00750

Zwaneveld N. A. A. ; Pawlak R. ; Abel M. ; Catalin D. ; Gigmes D. ; Bertin D. ; Porte L. Organized formation of 2D extended covalent organic frameworks at surfaces . J. Am. Chem. Soc. , 2008 , 130 ( 21 ), 6678 - 6679 . doi: 10.1021/ja800906f http://dx.doi.org/10.1021/ja800906f

Chen C. ; Joshi T. ; Li H. F. ; Chavez A. D. ; Pedramrazi Z. ; Liu P. N. ; Li H. ; Dichtel W. R. ; Bredas J. L. ; Crommie M. F. Local electronic structure of a single-layer porphyrin-containing covalent organic framework . ACS Nano , 2018 , 12 ( 1 ), 385 - 391 . doi: 10.1021/acsnano.7b06529 http://dx.doi.org/10.1021/acsnano.7b06529

Sun J. H. ; Klechikov A. ; Moise C. ; Prodana M. ; Enachescu M. ; Talyzin A. V. A molecular pillar approach to grow vertical covalent organic framework nanosheets on graphene: hybrid materials for energy storage . Angew. Chem. Int. Ed. , 2018 , 57 ( 4 ), 1034 - 1038 . doi: 10.1002/anie.201710502 http://dx.doi.org/10.1002/anie.201710502

Mitra S. ; Kandambeth S. ; Biswal B. P. ; Abdul K. M. ; Choudhury C. K. ; Mehta M. ; Kaur G. ; Banerjee S. ; Prabhune A. ; Verma S. ; Roy S. ; Kharul U. K. ; Banerjee R. Self-exfoliated guanidinium-based ionic covalent organic nanosheets (iCONs) . J. Am. Chem. Soc. , 2016 , 138 ( 8 ), 2823 - 2828 . doi: 10.1021/jacs.5b13533 http://dx.doi.org/10.1021/jacs.5b13533

Wang S. ; Wang Q. Y. ; Shao P. P. ; Han Y. Z. ; Gao X. ; Ma L. ; Yuan S. ; Ma X. J. ; Zhou J. W. ; Feng X. ; Wang B. Exfoliation of covalent organic frameworks into few-layer redox-active nanosheets as cathode materials for lithium-ion batteries . J. Am. Chem. Soc. , 2017 , 139 ( 12 ), 4258 - 4261 . doi: 10.1021/jacs.7b02648 http://dx.doi.org/10.1021/jacs.7b02648

Peng Y. W. ; Huang Y. ; Zhu Y. H. ; Chen B. ; Wang L. Y. ; Lai Z. C. ; Zhang Z. C. ; Zhao M. T. ; Tan C. L. ; Yang N. L. ; Shao F. W. ; Han Y. ; Zhang H. Ultrathin two-dimensional covalent organic framework nanosheets: Preparation and application in highly sensitive and selective DNA detection . J. Am. Chem. Soc. , 2017 , 139 ( 25 ), 8698 - 8704 . doi: 10.1021/jacs.7b04096 http://dx.doi.org/10.1021/jacs.7b04096

Guo Y. Y. ; Zhang Q. ; Gao S. Q. ; Wang H. Y. ; Li Z. Y. ; Qiu J. K. ; Zhao Y. ; Liu Z. M. ; Wang J. J. Bi-functional ionic liquids facilitate liquid-phase exfoliation of porphyrin-based covalent organic frameworks in water for highly efficient CO 2 photoreduction . Green Chem. , 2022 , 24 ( 24 ), 9530 - 9541 . doi: 10.1039/d2gc03194a http://dx.doi.org/10.1039/d2gc03194a

Zhang L. ; Zhu Q. H. ; Zhou Y. R. ; Wang S. L. ; Fu J. ; Liu J. Y. ; Zhang G. H. ; Ma L. J. ; Tao G. H. ; Tao G. H. ; He L. Hydrogen-bonding and π - π interaction promoted solution-processable covalent organic frameworks . Nat. Commun. , 2023 , 14 ( 1 ), 8181 . doi: 10.1038/s41467-023-43905-9 http://dx.doi.org/10.1038/s41467-023-43905-9

Mitra S. ; Sasmal H. S. ; Kundu T. ; Kandambeth S. ; Illath K. ; Díaz Díaz D. ; Banerjee R. Targeted drug delivery in covalent organic nanosheets (CONs) via sequential postsynthetic modification . J. Am. Chem. Soc. , 2017 , 139 ( 12 ), 4513 - 4520 . doi: 10.1021/jacs.7b00925 http://dx.doi.org/10.1021/jacs.7b00925

Zhang J. ; Han X. ; Wu X. W. ; Liu Y. ; Cui Y. Multivariate chiral covalent organic frameworks with controlled crystallinity and stability for asymmetric catalysis . J. Am. Chem. Soc. , 2017 , 139 ( 24 ), 8277 - 8285 . doi: 10.1021/jacs.7b03352 http://dx.doi.org/10.1021/jacs.7b03352

Evans A. M. ; Bradshaw N. P. ; Litchfield B. ; Strauss M. J. ; Seckman B. ; Ryder M. R. ; Castano I. ; Gilmore C. ; Gianneschi N. C. ; Mulzer C. R. ; Hersam M. C. ; Dichtel W. R. High-sensitivity acoustic molecular sensors based on large-area, spray-coated 2D covalent organic frameworks . Adv. Mater. , 2020 , 32 ( 42 ), 2004205 . doi: 10.1002/adma.202004205 http://dx.doi.org/10.1002/adma.202004205

Li J. L. ; Cheng Z. L. ; Wang Z. Y. ; Dong J. C. ; Jiang H. C. ; Wang W. J. ; Zou X. Q. ; Zhu G. S. Ultramicroporous covalent organic framework nanosheets with functionality pair for membrane C 2 H 2 /C 2 H 4 separation . Angew. Chem. Int. Ed., 2023, 62 ( 10 ), e 202216675 . doi: 10.1002/anie.202216675 http://dx.doi.org/10.1002/anie.202216675

Wang J. F. ; Zhang X. M. ; Shen R. C. ; Yuan Q. ; Yang Y. B. Staggered-stacking two-dimensional covalent organic framework membranes for molecular and ionic sieving . ACS Nano , 2024 , 18 ( 51 ), 34698 - 34707 . doi: 10.1021/acsnano.4c10274 http://dx.doi.org/10.1021/acsnano.4c10274

Paul S. ; Gupta M. ; Mahato A. K. ; Karak S. ; Basak A. ; Datta S. ; Banerjee R. ; Covalent organic frameworks for the purification of recombinant enzymes and heterogeneous biocatalysis . J. Am. Chem. Soc. , 2024 , 146, 858 - 867 . doi: 10.1021/jacs.3c11169 http://dx.doi.org/10.1021/jacs.3c11169

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Related Institution

东华大学材料科学与工程学院，纤维材料改性国家重点实验室，上海松江

State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University

Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, Center for Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Peking University

Shanghai Institute of Applied Physics, Chinese Academy of Sciences

University of Chinese Academy of Sciences

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Liquid-phase Exfoliation of Pyridine-based Covalent Organic Framework Nanosheets for High-performance H2/CO2 Gas Separation Membrane Fabrication

DOI：10.11777/j.issn1000-3304.2025.25003

摘要

Abstract

关键词

Keywords

references

Liquid-phase Exfoliation of Pyridine-based Covalent Organic Framework Nanosheets for High-performance H₂/CO₂ Gas Separation Membrane Fabrication