高级检索

    刘程, 李国宁, 张曼霞, 翁志焕, 蹇锡高. 基于卟啉基多孔有机聚合物的CO2吸附及催化性能[J]. 功能高分子学报, 2020, 33(6): 532-539. doi: 10.14133/j.cnki.1008-9357.20200116001
    引用本文: 刘程, 李国宁, 张曼霞, 翁志焕, 蹇锡高. 基于卟啉基多孔有机聚合物的CO2吸附及催化性能[J]. 功能高分子学报, 2020, 33(6): 532-539. doi: 10.14133/j.cnki.1008-9357.20200116001
    LIU Cheng, LI Guoning, ZHANG Manxia, WENG Zhihuan, JIAN Xigao. CO2 Adsorption and Catalytic Performance of Porphyrin-Based Porous Organic Polymers[J]. Journal of Functional Polymers, 2020, 33(6): 532-539. doi: 10.14133/j.cnki.1008-9357.20200116001
    Citation: LIU Cheng, LI Guoning, ZHANG Manxia, WENG Zhihuan, JIAN Xigao. CO2 Adsorption and Catalytic Performance of Porphyrin-Based Porous Organic Polymers[J]. Journal of Functional Polymers, 2020, 33(6): 532-539. doi: 10.14133/j.cnki.1008-9357.20200116001

    基于卟啉基多孔有机聚合物的CO2吸附及催化性能

    CO2 Adsorption and Catalytic Performance of Porphyrin-Based Porous Organic Polymers

    • 摘要: 为了实现在温和环境及无助催化剂的条件下高效催化CO2 与环氧烷烃的环加成反应,设计合成了两种卟啉基多孔有机聚合物—含羧基的卟啉基多孔有机聚合物(PPOP-COOH)和含季铵盐离子对的卟啉基多孔有机聚合物(PPOP-I),通过前修饰和后修饰的方式分别在聚合物中引入季铵盐阴阳离子对亲核基团和金属活性中心。通过红外光谱和物理吸附仪表征了聚合物的化学结构和孔结构,研究了其作为催化剂对催化CO2与环氧烷烃的环加成反应的影响。研究结果表明,这两种聚合物均具有多级孔结构,比表面积为302~514 m2/g,聚合物中的路易斯酸金属离子、亲核试剂和多级孔结构的协同作用大大促进了CO2与环氧烷烃的环加成反应,在较为温和的条件(80 ℃、0.3 MPa、24 h)下,反应的选择性和转化率均达到99%以上;聚合物在多次重复使用后,依然具有很好的催化性能。

       

      Abstract: In order to achieve high efficiency in the cycloaddition reaction of CO2 under the conditions of mild environment and absence of cocatalyst, two kinds of porphyrin-based porous organic polymers (PPOP-COOH and PPOP-I) were designed and synthesized in this paper. The nucleophilic groups and metal active centers of quaternary ammonium salts were introduced into the polymers by means of pre-modification and post-modification. The two crosslinked polymers showed excellent chemical and thermal stability. The chemical structures and pore structures of the two polymers were characterized, and both of them had hierarchical porous structure with specific surface areas of 302—514 m2/g. Under the condition of 298 K, CO2 adsorption and desorption tests were carried out, and the results showed that CO2 adsorption capacity of carboxyl-containing polymer was greater than that of quaternary ammonium salt containing polymer. The effect of the catalyst on the cycloaddition reaction of CO2 was studied. The results showed that the synergistic effect of Lewis acid metal ions, nucleophiles and multi-pore structure greatly promoted the CO2 cycloaddition reaction. Under moderate conditions (80 ℃, 0.3 MPa, 24 h), the reaction selectivity and conversion were more than 99%, and the polymers still presented good catalytic performances after being reused for many times.

       

    /

    返回文章
    返回