Nitrogen-Containing Microporous Conjugated Polymers via Carbazole-Based Oxidative Coupling Polymerization: Preparation, Porosity, and Gas Uptake
Nitrogen-Containing Microporous Conjugated Polymers via Carbazole-Based Oxidative Coupling Polymerization: Preparation, Porosity, and Gas Uptake
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基于咔唑氧化偶联聚合的含氮微孔共轭聚合物：制备、孔隙率和气体吸收
DOI：
10.1002/smll.201301618
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发表时间：
2014-01-29
期刊：
影响因子：
13.3
通讯作者：
Han, Bao-Hang
中科院分区：
文献类型：
--
作者：
Chen, Qi;Liu, De-Peng;Han, Bao-Hang
报道了利用咔唑基氧化偶联聚合制备微孔共轭聚咔唑的简便方法。形成聚合物网络的过程具有成本效益优势，例如使用廉价的催化剂，温和的反应条件，并且需要单一的单体。由于偶联聚合不需要其他官能团，如光环基团、硼酸和炔，因此单体的性质很可能被完全保留，最终聚合物的结构也更容易表征。以非平面刚性构象为构建单元，合成了一系列具有永久孔隙度的微孔共轭聚咔唑（CPOP‐2-7）。这些多孔材料的brunauer - emmet - teller比表面积值在510和1430 m2g−1之间变化。基于不同构建块的聚合物的主要孔径位于0.59至0.66 nm之间。气体（h2和CO2）吸附等温线表明，cpop‐7对氢气（1.0 bar和77 K时为1.51 wt%）和二氧化碳（1.0 bar和273 K时为13.2 wt%）的吸附能力最好。此外，其高的CH4/ n2和CO2/ n2吸附选择性使聚合物cpop‐7在气体分离方面具有潜在的应用前景。
Facile preparation of microporous conjugated polycarbazoles via carbazole‐based oxidative coupling polymerization is reported. The process to form the polymer network has cost‐effective advantages such as using a cheap catalyst, mild reaction conditions, and requiring a single monomer. Because no other functional groups such as halo groups, boric acid, and alkyne are required for coupling polymerization, properties derived from monomers are likely to be fully retained and structures of final polymers are easier to characterize. A series of microporous conjugated polycarbazoles (CPOP‐2–7) with permanent porosity are synthesized using versatile carbazolyl‐bearing 2D and 3D conjugated core structures with non‐planar rigid conformation as building units. The Brunauer–Emmett–Teller specific surface area values for these porous materials vary between 510 and 1430 m2g−1. The dominant pore sizes of the polymers based on the different building blocks are located between 0.59 and 0.66 nm. Gas (H2and CO2) adsorption isotherms show thatCPOP‐7exhibits the best uptake capacity for hydrogen (1.51 wt% at 1.0 bar and 77 K) and carbon dioxide (13.2 wt% at 1.0 bar and 273 K) among the obtained polymers. Furthermore, its high CH4/N2and CO2/N2adsorption selectivity gives polymerCPOP‐7potential application in gas separation.