The role of the internal molecular free volume in defining organic porous copolymer properties: tunable porosity and highly selective CO2 adsorption
The role of the internal molecular free volume in defining organic porous copolymer properties: tunable porosity and highly selective CO2 adsorption
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内部分子自由体积在定义有机多孔共聚物特性中的作用：可调孔隙率和高选择性 CO2 吸附
DOI：
10.1039/c6cp00981f
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发表时间：
2016
影响因子：
3.3
通讯作者：
Pan Chunyue
中科院分区：
文献类型：
--
作者：
Zhang Yindong;Zhu Yunlong;Guo Jun;Gu Shuai;Wang Yuanyuan;Fu Yu;Chen Dongyang;Lin Yijun;Yu Guipeng;Pan Chunyue
公开了一系列具有可调永久微孔性和高选择性二氧化碳捕获的新型偶氮官能化共聚网络（简称NOP-34系列）。该合成是通过Zn诱导的具有不同“内部分子自由体积”（IMFV）的两种硝基苯类结构单元的还原交叉偶联共聚来完成的，即，2，7，14-三硝基三蝶烯和2，2 ′，7，7 ′-四硝基-9，9 ′-螺二芴。增加螺二芴（SBF）片段的含量与较小的IMFV相对于三蝶烯导致非常规的上升-下降模式的孔隙度。与大多数报道的表面积介于相应均聚物之间的多孔共聚物不同，具有30%SBF链段的共聚物NOP-34@7030前所未有地显示出最大的Brunauer-Emmett-Teller比表面积（高达823 m2 g−1）以及促进的CO2吸收能力（在273 K/1.0 bar下从2.31至3.22 mmol g−1）。具有中等表面积的100%三蝶烯（TPC）衍生的均聚物（NOP-34@1000）在五种样品中显示出最高的CO2/N2 IAST选择性109（273 K），超过了大多数已知的纳米多孔有机聚合物。这可能有助于我们理解IMFV与共聚材料性能的关系。
A series of novel azo-functionalized copolymerized networks (simply known as NOP-34 series) with tunable permanent microporosity and highly selective carbon dioxide capture are disclosed. The synthesis was accomplished by Zn-induced reductive cross-coupling copolymerization of two nitrobenzene-like building blocks with different ‘internal molecular free volumes’ (IMFVs), i.e., 2,7,14-trinitrotriptycene and 2,2′,7,7′-tetranitro-9,9′-spirobifluorene, with different molar ratios. Increasing the content of spirobifluorene (SBF) segments with a smaller IMFV relative to that of triptycene leads to an unconventional rise–fall pattern in porosity. Unlike most reported porous copolymers whose surface area lies between the corresponding homopolymers, the copolymer NOP-34@7030 with 30% SBF segments unprecedentedly shows the largest Brunauer–Emmett–Teller specific surface area (up to 823 m2 g−1) as well as promoted CO2 uptake abilities (from 2.31 to 3.22 mmol g−1, at 273 K/1.0 bar). The 100% triptycene(TPC)-derived homopolymer (NOP-34@1000) with a moderate surface area shows the highest CO2/N2 IAST selectivity of 109 (273 K) among the five samples, surpassing most known nanoporous organic polymers. This may contribute significantly to our understanding of the relationship of IMFVs with the properties of copolymerized materials.