Kilogram-scale Flux Synthesis of Olefin-linked Amorphous Conjugated Microporous Polymers toward C2H2/CO2 Separation

Yu-Shu Zhang; Kai-Yuan Wang; Li-Qin Hao; Ji-Xian Wang; Meng-Jin Wang; Yao Chen; Peng Cheng; Xia Li; Zhen-Jie Zhang

doi:10.1007/s10118-025-3437-0

Your Location：

Home >

Browse articles >

Kilogram-scale Flux Synthesis of Olefin-linked Amorphous Conjugated Microporous Polymers toward C₂H₂/CO₂ Separation

RESEARCH ARTICLE | Updated：2026-04-30

- Kilogram-scale Flux Synthesis of Olefin-linked Amorphous Conjugated Microporous Polymers toward C₂H₂/CO₂ Separation
- Chinese Journal of Polymer Science Vol. 44, Issue 5, Pages: 1364-1372(2026)
- Affiliations：
  
  a.College of Chemistry, State Key Laboratory of Medicinal Chemical Biology, Nankai University, Tianjin 300071, China
  b.Key Laboratory of Advanced Energy Materials Chemistry, Ministry of Education, Nankai University, Tianjin 300071, China
  c.College of Pharmacy, Nankai University, Tianjin 300071, China
  d.Frontiers Science Center for New Organic Matter, Renewable Energy Conversion and Storage Center, Nankai University, Tianjin 300071, China
  e.Nankai International Advanced Research Institute (Shenzhen Futian), Nankai University, Tianjin 300071, China
  f.Nankai Cangzhou Bohai New Area Green Chemical Research Co., LTD., Cangzhou 061100, China
- Author bio：
  
  zhangzhenjie@nankai.edu.cn
- Funds：
- DOI：10.1007/s10118-025-3437-0
  CLC：
- Received：06 July 2025，
  
  Accepted：17 August 2025，
  
  Online First：22 December 2025，
  
  Published：05 May 2026
- Accepted：
Scan QR Code
Zhang, Y. S.; Wang, K. Y.; Hao, L. Q.; Wang, J. X.; Wang, M. J.; Chen, Y.; Cheng, P.; Li, X.; Zhang, Z. J. Kilogram-scale flux synthesis of olefin-linked amorphous conjugated microporous polymers toward C₂H₂/CO₂ separation. Chinese J. Polym. Sci. 2026, 44, 1364–1372 DOI: 10.1007/s10118-025-3437-0.

Yu-Shu Zhang, Kai-Yuan Wang, Li-Qin Hao, et al. Kilogram-scale Flux Synthesis of Olefin-linked Amorphous Conjugated Microporous Polymers toward C₂H₂/CO₂ Separation[J]. Chinese Journal of Polymer Science, 2026, 44(5): 1364-1372. DOI: 10.1007/s10118-025-3437-0.
Zhang, Y. S.; Wang, K. Y.; Hao, L. Q.; Wang, J. X.; Wang, M. J.; Chen, Y.; Cheng, P.; Li, X.; Zhang, Z. J. Kilogram-scale flux synthesis of olefin-linked amorphous conjugated microporous polymers toward C₂H₂/CO₂ separation. Chinese J. Polym. Sci. 2026, 44, 1364–1372 DOI: 10.1007/s10118-025-3437-0. DOI：

Yu-Shu Zhang, Kai-Yuan Wang, Li-Qin Hao, et al. Kilogram-scale Flux Synthesis of Olefin-linked Amorphous Conjugated Microporous Polymers toward C₂H₂/CO₂ Separation[J]. Chinese Journal of Polymer Science, 2026, 44(5): 1364-1372. DOI: 10.1007/s10118-025-3437-0. DOI：

摘要

This work presents a solvent-free flux synthesis of olefin-linked CMPs

offering a scalable and environmentally friendly alternative to traditional methods. Notably

NKCMP-1 was successfully synthesized on a kilogram scale (0.54 kg) while preserving high surface area and uniform microporosity. The materials exhibit excellent C

/CO

selectivity and stability

demonstrating great potential for industrial gas separation.

Abstract

Conjugated microporous polymers (CMPs) have demonstrated significant potential for gas separation due to their permanent microporosity

high adsorption capacity

and exceptional chemical robustness. However

the scalable

cost-effective and environmentally friendly synthesis of CMPs as an alternative to energy-intensive traditional solvothermal methods remains underexplored. Herein

we present a solvent-free

flux synthesis method for constructing olefin-linked amorphous CMPs (NKCMP-1 and NKCMP-2) through Knoevenagel condensation of 2

6-tetramethylpyrazine with linear aromatic aldehydes. This method surpasses ion

othermal and mechanochemical routes in terms of scalability and product uniformity. Notably

NKCMP-1 can be synthesized on a kilogram scale (0.54 kg) while maintaining structural integrity

high surface area and a uniform microporous architecture. Both NKCMP-1 and NKCMP-2 exhibit outstanding C

/CO

selectivity and cyclic stability under ambient conditions

as confirmed by dynamic breakthrough experiments. These features make the developed CMPs highly promising for real-world industrial gas purification applications.

关键词

Keywords

references

Lee, J.-S. M.; Cooper, A. I. Advances in conjugated microporous Polymers. Chem. Rev. 2020 , 120 , 2171−2214..

Xu, Y.; Jin, S.; Xu, H.; Nagai, A.; Jiang, D. Conjugated microporous polymers: design, synthesis and application. Chem. Soc. Rev. 2013 , 42 , 8012−8031..

Mohamed, M. G.; El-Mahdy, A. F. M.; Kotp, M. G.; Kuo, S. W. Advances in porous organic polymers: syntheses, structures, and diverse applications. Mater. Adv. 2022 , 3 , 707−733..

Mohamed, M. G.; Atayde, E. C.; Matsagar, B. M.; Na, J.; Yamauchi, Y.; Wu, K. C. W.; Kuo, S. W. Construction hierarchically mesoporous/microporous materials based on block copolymer and covalent organic framework. J. Taiwan Inst. Chem. Eng. 2020 , 112 , 180−192..

Mohamed, M. G.; Chen, C. C.; Kuo, S. W. Nitrogen and sulfur co-doped microporous carbon through benzo[c ] -1,2,5-thiadiazole-functionalized benzoxazine-linkage porous organic polymer in CO 2 capture and energy storage. React. Funct. Polym. 2025 , 214 , 106286..

Dawson, R.; Adams, D. J.; Cooper, A. I. Chemical tuning of CO 2 sorption in robust nanoporous organic polymers. Chem. Sci. 2011 , 2 , 1173−1177..

[Ejaz, M.; Mohamed, M. G.; Kuo, S. W. Benzoxazine-linked polyhedral oligomeric silsesquioxane: 3D porous organic-inorganic polymer for improved CO 2 capture and supercapacitor performance. J. Taiwan Inst. Chem. Eng . 2025 , 106098..

Daliran, S.; Oveisi, A. R.; Peng, Y.; López-Magano, A.; Khajeh, M.; Mas-Ballesté, R.; Alemán, J.; Luque, R.; Garcia, H. Metal–organic framework (MOF)-, covalent-organic framework (COF)-, a nd porous-organic polymers (POP)-catalyzed selective C–H bond activation and functionalization reactions. Chem. Soc. Rev. 2022 , 51 , 7810−7882..

Chen, L.; Yang, Y.; Jiang, D. CMPs as scaffolds for constructing porous catalytic frameworks: a built-in heterogeneous catalyst with high activity and selectivity based on nanoporous metalloporphyrin polymers. J. Am. Chem. Soc. 2010 , 132 , 9138−9143..

Mohamed, M. G.; Chen, C. C.; Ibrahim, M.; Osama Mousa, A.; Elsayed, M. H.; Ye, Y.; Kuo, S. W. Tetraphenylanthraquinone and dihydroxybenzene-tethered conjugated microporous polymer for enhanced CO 2 uptake and supercapacitive energy storage. JACS Au 2024 , 4 , 3593−3605..

Singh, P. N.; Mohamed, M. G.; Kotp, M. G.; Mondal, T.; Chaganti, S. V.; Ibrahim, M.; Sharma, S. U.; Ye, Y.; Kuo, S. W. Nitrogen- and sulfur-richmicroporous carbons derived from conjugated microporous polymers for CO 2 uptake, supercapacitor energy storage, and electrochemical hydrogen production. ACS Appl. Polym. Mater. 2025 , 7 , 3324−3336..

Taylor, D.; Dalgarno, S. J.; Xu, Z.; Vilela, F. Conjugated porous polymers: incredibly versatile materials with far-reaching applications. Chem. Soc. Rev. 2020 , 49 , 3981−4042..

Jiang, J.-X.; Su, F.; Trewin, A.; Wood, C. D.; Campbell, N. L.; Niu, H.; Dickinson, C.; Ganin, A. Y.; Rosseinsky, M. J.; Khimyak, Y. Z.; Cooper, A. I. Conjugated microporous poly(aryleneethynylene) networks. Angew. Chem. Int. Ed. 2007 , 46 , 8574−8578..

Weber, J.; Thomas, A. Toward stable interfaces in conjugated polymers: microporous poly(p-phenylene) and poly(phenyleneethynylene) based on a spirobifluorene building block. J. Am. Chem. Soc. 2008 , 130 , 6334−6335..

Schmidt, J.; Werner, M.; Thomas, A. Conjugated microporous polymer networks via Yamamoto polymerization. Macromolecules 2009 , 42 , 4426−4429..

Ren, S.; Bojdys, M. J.; Dawson, R.; Laybourn, A.; Khimyak, Y. Z.; Adams, D. J.; Cooper, A. I. Porous, fluorescent, covalent triazine-based frameworks via room-temperature and microwave-assisted synthesis. Adv. Mater. 2012 , 24 , 2357−2361..

Dey, A.; Chakraborty, S.; Singh, A.; Rahimi, F. A.; Biswas, S.; Mandal, T.; Maji, T. K. Microwave a ssisted fast synthesis of a donor-acceptor COF towards photooxidative amidation catalysis. Angew. Chem. Int. Ed. 2024 , 63 , e202403093..

Li, Q.; Wang, Z. M.; Chen, Y.; Wang, Y. R.; Guo, C.; Huang, Q.; Dong, L. Z.; Li, S. L.; Lan, Y. Q. CO 2 -to-CH 4 electroreduction over scalable Cu-porphyrin based organic polymers promoted by direct auxiliary bonding interaction. J. Mater. Chem. A. 2022 , 10 , 25356−25362..

Kim, J.; Moisanu, C. M.; Gannett, C. N.; Halder, A.; Fuentes-Rivera, J. J.; Majer, S. H.; Lancaster, K. M.; Forse, A. C.; Abruña, H. D.; Milner, P. J. Conjugated microporous polymers via solvent-free ionothermal cyclotrimerization of methyl ketones. Chem. Mater. 2021 , 33 , 8334−8342..

Maschita, J.; Banerjee, T.; Savasci, G.; Haase, F.; Ochsenfeld, C.; Lotsch, B. V. Ionothermal synthesis of imide-linked covalent organic frameworks. Angew. Chem. Int. Ed. 2020 , 59 , 15750−15758..

Cui, K.; Tang, X.; Xu, X.; Kou, M.; Lyu, P.; Xu, Y. Crystalline dual-porous covalent triazine frameworks as a new platform for efficient electrocatalysis. Angew. Chem. Int. Ed. 2024 , 63 , e202317664..

Lloyd, E. M.; Vakil, J. R.; Yao, Y.; Sottos, N. R.; Craig, S. L. Covalent mechanochemistry and contemporary polymer network chemistry: a marriage in the making. J. Am. Chem. Soc. 2023 , 145 , 751−768..

Troschke, E.; Grätz, S.; Lübken, T.; Borchardt, L. Mechanochemical Friedel–Crafts alkylation—a sustainable pathway towards porous organic polymers. Angew. Chem. Int. Ed. 2017 , 56 , 6859−6863..

Krusenbaum, A.; Grätz, S.; Tigineh, G. T.; Borchardt, L.; Kim, J. G. The mechanochemical synthesis of polymers. Chem. Soc. Rev. 2022 , 51 , 2873−2905..

Wang, Z.; Zhang, Y.; Wang, T.; Hao, L.; Lin, E.; Chen, Y.; Cheng, P.; Zhang, Z. Organic flux synthesis of covalent organic frameworks. Chem 2023 , 9 , 2178−2193..

Jia, H.; Yao, N.; Jin, Y.; Wu, L.; Zhu, J.; Luo, W. Stabilizing atomic Ru species in conjugated sp 2 carbon-linked covalent organic framework for acidic water oxidation. Nat. Commun. 2024 , 15 , 5419..

He, T.; On, I. K. W.; Bi, S.; Huang, Z.; Guo, J.; Wang, Z.; Zhao, Y. Crystalline olefin-linked chiral covalent organic frameworks as a platform for asymmetric catalysis. Angew. Chem. Int. Ed. 2024 , 63 , e202405769..

Fu, G.; Yang, D.; Xu, S.; Li, S.; Zhao, Y.; Yang, H.; Wu, D.; Petkov, P. S.; Lan, Z.-A.; Wang, X.; Zhang, T. Construction of thiadiazole-bridged sp 2 -carbon-conjugated covalent organic frameworks with diminished excitation binding energy toward superior photocatalysis. J. Am. Chem. Soc. 2024 , 146 , 1318−1325..

Yan, Q.; Tao, S.; Liu, R.; Zhi, Y.; Jiang, D. Crystalline, porous helicene covalent organic frameworks. Angew. Chem. Int. Ed. 2024 , 63 , e202316092..

Wang, Z.; Yang, Y.; Zhao, Z.; Zhang, P.; Zhang, Y.; Liu, J.; Ma, S.; Cheng, P.; Chen, Y.; Zhang, Z. Green synthesis of olefin-linked covalent organic frameworks for hydrogen fuel cell applications. Nat. Commun. 2021 , 12 , 1982..

Zhang, P.; Wang, Z.; Wang, S.; Wang, J.; Liu, J.; Wang, T.; Chen, Y.; Cheng, P.; Zhang, Z. Fabricating industry-compatible olefin-linked COF resins for oxoanion pollutant scavenging. Angew. Chem. Int. Ed. 2022 , 61 , e202213247..

Yang, Y.; Wang, S.; Duan, Y.; Wang, T.; Wang, F.; Zhu, H.; Wang, Z.; Zhang, K.; Cheng, P.; Zhang, Z. Flux synthesis of robust polyimide covalent organic frameworks with high-density redox sites for efficient proton batteries. Angew. Chem. Int. Ed. 2025 , 64 , e202418394..

Wang, Z.; Zhang, Y.; Wang, T.; Lin, E.; Wang, T.; Chen, Y.; Cheng, P.; Zhang, Z. Modulating the interlayer stacking of covalent organic frameworks for efficient acetylene separation. Small 2023 , 19 , 2303684..

Zhao, Z.; Chen, X.; Li, B.; Zhao, S.; Niu, L.; Zhang, Z.; Chen, Y. Spatial regulation of acceptor units in olefin-linked COFs toward highly efficient photocatalytic H 2 evolution. Adv. Sci. 2022 , 9 , 2203832..

Wang, Z.; Zhang, Y.; Liu, J.; Chen, Y.; Cheng, P.; Zhang, Z. Flux synthesis of two-dimensional covalent organic frameworks. Nat. Protoc. 2024 , 19 , 3489−3519..

Lin, J.; Bi, S.; Fan, Z.; Fu, Z.; Meng, Z.; Hou, Z.; Zhang, F. A metal-free approach to bipyridinium salt-based conjugated porous polymers with olefin linkages. Polym. Chem. 2021 , 12 , 1661−1667..

Li, X.; Zou, Y.; Jia, Z.; Zhang, J.; Li, Y.; Guo, X.; Zhang, M.; Li, K.; Li, J.; Ma, L. A fully conjugated organic polymer via Knoevenagel condensation for fast separation of uranium. J. Hazard. Mater. 2021 , 401 , 123802..

Hu, R.; Hassan, M.; Liu, L.; Zhang, S.; Gong, W. Pyrylium-based porous organic polymers via Knoevenagel condensation for efficient visible-light-driven heterogeneous photodegradation. Chin. Chem. Lett. 2023 , 34 , 107541..

Kumar, P.; Maji, B. A phosphorus-based olefin linked fully conjugated polymeric ligand for palladium-catalyzed trans-selective dicarbofunctionalization of internal alkynes. J. Mater. Chem. A 2023 , 11 , 20752−20760..

Zhuang, X.; Zhao, W.; Zhang, F.; Cao, Y.; Liu, F.; Bi, S.; Feng, X. A two-dimensional conjugated polymer framework with fully sp 2 -bonded carbon skeleton. Polym. Chem. 2016 , 7 , 4176−4181..

Jiang, J.-X.; Su, F.; Trewin, A.; Wood, C. D.; Niu, H.; Jones, J. T. A.; Khimyak, Y. Z.; Cooper, A. I. Synthetic control of the pore dimension and surface area in conjugated microporous polymer and copolymer networks. J. Am. Chem. Soc. 2008 , 130 , 7710−7720..

[Jiang, J. X.; Su, F.; Niu, H.; Wood, C. D.; Campbell, N. L.; Khimyak, Y. Z.; Cooper, A. I. Conjugated microporous poly(phenylene butadiynylene)s. Chem. Commun . 2008 , 486-488..

Chen, Q.; Wang, Q.; Luo, M.; Mao, L. J.; Yan, C. G.; Li, Z. H.; Han, B. H. Microporous polymeric microsphere via surfactant-free Suzuki coupling polymerization in a single-phase: porosity and gas uptake. Polymer 2012 , 53 , 2032−2037..

Tsyurupa, M. P.; Davankov, V. A. Porous structure of hypercrosslinked polystyrene: state-of-the-art mini-review. React. Funct. Polym. 2006 , 66 , 768−779..

[Germain, J.; Fréchet, J. M. J.; Svec, F. Nanoporous, hypercrosslinked polypyrroles: effect of crosslinking moiety on pore size and selective gas adsorption. Chem. Commun . 2009 , 1526-1528.

Germain, J.; Fréchet, J. M. J.; Svec, F. Hypercrosslinked polyanilines with nanoporous structure and high surface area: potential adsorbents for hydrogen storage. J. Mater. Chem. 2007 , 17 , 4989−4997..

Zhang, Z.; Peh, S. B.; Krishna, R.; Kang, C.; Chai, K.; Wang, Y.; Shi, D.; Zhao, D. Optimal pore chemistry in an ultramicroporous metal–organic framework for benchmark inverse CO 2 /C 2 H 2 separation. Angew. Chem. Int. Ed. 2021 , 60 , 17198−17204..

Zhang, Y.; Sun, W.; Luan, B.; Li, J.; Luo, D.; Jiang, Y.; Wang, L.; Chen, B. Topological design of unprecedented metal-organic frameworks featuring multiple anion functionalities and hierarchical porosity for benchmark acetylene separation. Angew. Chem. Int. Ed. 2023 , 62 , e202309925..

Ye, Y.; Xian, S.; Cui, H.; Tan, K.; Gong, L.; Liang, B.; Pham, T.; Pandey, H.; Krishna, R.; Lan, P. C.; Forrest, K. A.; Space, B.; Thonhauser, T.; Li, J.; Ma, S. Metal–organic framework based hydrogen-bonding nanotrap for efficient acetylene storage and separation. J. Am. Chem. Soc. 2022 , 144 , 1681−1689..

Yang, Y.; Lin, E.; Wan g, S.; Wang, T.; Wang, Z.; Zhang, Z. Single-crystal one-dimensional porous ladder covalent polymers. J. Am. Chem. Soc. 2024 , 146 , 782−790..

Wang, L.; Huang, H.; Zhang, X.; Zhao, H.; Li, F.; Gu, Y. Designed metal-organic frameworks with potential for multi-component hydrocarbon separation. Coord. Chem. Rev. 2023 , 484 , 215111..

Wang, T.; Lin, E.; Peng, Y. L.; Chen, Y.; Cheng, P.; Zhang, Z. Rational design and synthesis of ultramicroporous metal-organic frameworks for gas separation. Coord. Chem. Rev. 2020 , 423 , 213485..

Views

126

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Molecularly Engineered Contorted Polyimides: Unraveling the Role of Backbone Rigidity in Gas Separation

Research Progress in the Fabrication of Covalent Organic Framework Membranes for Chemical Separations

Bioinspired Zinc-doped Nano Hydroxyapatite Reinforced Poly(lactic acid) Composites for Bone Repair

Manipulating Hierarchical Aggregation Structure via Film-forming Kinetics Enables Organic Photovoltaics over 20% Efficiency

Silk Sericin-inspired Poly-β-homoserine for Protein Protection

Related Author

Zhen-Jie Zhang

Hong-Qin Zhao

Bing-Yu Zou

Bing-Xi He

Wei-Feng Peng

Lu-Hao Qiu

Feng Bao

Ming-Jun Huang

Related Institution

Nankai Cangzhou Bohai New Area Green Chemical Research Co., LTD

Guangdong Provincial Key Laboratory of Functional and Intelligent Hybrid Materials and Devices, Guangdong Basic Research Center of Excellence for Energy and Information Polymer Materials, South China University of Technology

State Key Laboratory of Green and Efficient Development of Phosphorus Resources

Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, College of Chemistry, Chemical Engineering and Materials Science, Soochow University

School of Emergent Soft Matter, State Key Laboratory of Advanced Papermaking and Paper-based Materials, South China University of Technology

⁰