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<p>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 2,3,5,6-tetramethylpyrazine with linear aromatic aldehydes. This method surpasses ionothermal 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<sub>2</sub>H<sub>2</sub>/CO<sub>2</sub> 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.</p>

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

  • 期刊论文

  • 发表日期：

    2025年12月22日

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

摘要

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 2,3,5,6-tetramethylpyrazine with linear aromatic aldehydes. This method surpasses ionothermal 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 C2H2/CO2 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.