物理化学学报 >> 2017, Vol. 33 >> Issue (9): 1898-1904.doi: 10.3866/PKU.WHXB201705112

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富羧酸基团的共轭微孔聚合物:结构单元对孔隙和气体吸附性能的影响

姚婵1,李国艳1,许彦红1,2,*()   

  1. 1 吉林师范大学,环境友好材料制备和应用教育部重点实验室,长春130103
    2 吉林师范大学,功能材料物理与化学教育部重点实验室,吉林四平136000
  • 收稿日期:2017-04-06 发布日期:2017-07-05
  • 通讯作者: 许彦红 E-mail:xuyh@jlnu.edu.cn
  • 基金资助:
    国家自然科学基金(21501065);吉林省科技发展计划(20160101319JC);吉林省教育厅科学技术研究项目(2015229);四平市科技发展计划项目(2015057)

Carboxyl-Enriched Conjugated Microporous Polymers: Impact of Building Blocks on Porosity and Gas Adsorption

Chan YAO1,Guo-Yan LI1,Yan-Hong XU1,2,*()   

  1. 1 Key Laboratory of Preparation and Applications of Environmental Friendly Materials of Ministry of Education, Jilin Normal University, Changchun 130103, P. R. China
    2 Key Laboratory of Functional Materials Physics and Chemistry of the Ministry of Education, Jilin Normal University, Siping 136000, Jilin Province, P. R. China
  • Received:2017-04-06 Published:2017-07-05
  • Contact: Yan-Hong XU E-mail:xuyh@jlnu.edu.cn
  • Supported by:
    the National Natural Science Foundation of China(21501065);Science and Technology Program of Jilin Province, China(20160101319JC);Science and Technology Research Program of the Education Department of Jilin Province(2015229);Science and Technology Program of Siping City(2015057)

摘要:

共轭微孔聚合物(CMPs)骨架中的孔和极性基团对聚合物的气体吸附性能起着重要作用。阐明聚合物中极性基团的效果对该领域的进一步发展是必不可少的。为了解决这个根本问题,我们使用最简单的芳香系统-苯作为建筑单体,构筑了两个新颖的富羧酸基团的CMPs(CMP-COOH@1,CMP-COOH@2),并探讨了CMPs中游离羧酸基团的量对其孔隙、吸附焓、气体吸附和选择性的深远影响。CMP-COOH@1和CMP-COOH@2显示的BET比表面积分别为835和765 m2·g-1。这两种聚合物在二氧化碳存储方面显示了高潜力。在273 K和1.05 × 105 Pa条件下,CMP-COOH@1和CMP-COOH@2的CO2吸附值分别为2.17和2.63 mmol·g-1。我们的研究结果表明,在相同的条件下增加聚合物中羧基基团的含量可以提高材料对气体的吸附容量和选择性。

关键词: 共轭微孔聚合物, 羧酸, 孔, 气体吸附, 选择性

Abstract:

Polar groups in the skeletons of conjugated microporous polymers (CMPs) play an important role in determining their porosity and gas sorption performance. Understanding the effect of the polar group on the properties of CMPs is essential for further advances in this field. To address this fundamental issue, we used benzene, the simplest aromatic system, as a monomer for the construction of two novel CMPs with multi-carboxylic acid groups in their skeletons (CMP-COOH@1 and CMP-COOH@2). We then explored the profound effect the amount of free carboxylic acid in each polymer had on their porosity, isosteric heat, gas adsorption, and gas selectivity. CMP-COOH@1 and CMP-COOH@2 showed Brunauer-Emmett-Teller (BET) surface areas of 835 and 765 m2·g-1, respectively, displaying high potential for carbon dioxide storage applications. CMP-COOH@1 and CMP-COOH@2 exhibited CO2 capture capabilities of 2.17 and 2.63 mmol·g-1 (at 273 K and 1.05 × 105 Pa), respectively, which were higher than those of their counterpart polymers, CMP-1 and CMP-2, which showed CO2 capture capabilities of 1.66 and 2.28 mmol·g-1, respectively. Our results revealed that increasing the number of carboxylic acid groups in polymers could improve their adsorption capacity and selectivity.

Key words: Conjugated Microporous Polymers, Carboxylic Acid, Pore, Gas Adsorption, Selectivity

MSC2000: 

  • O647