Cyclotetrabenzil-Based Porous Organic Polymers with High Carbon Dioxide Affinity
Cyclotetrabenzil-Based Porous Organic Polymers with High Carbon Dioxide Affinity
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DOI：
10.1055/a-1512-5753
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发表时间：
2021-04
影响因子：
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通讯作者：
T. Ashirov;Maymounah Alrayyani;K. Song;O. Miljanić;Ali Coskun
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文献类型：
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作者：
T. Ashirov;Maymounah Alrayyani;K. Song;O. Miljanić;Ali Coskun
摘要 近年来，人们对结合大环单元的多孔有机聚合物（POP）进行了研究，试图将大环的固有主客体性质转移到多孔网络上以实现复杂的分离。在这方面，具有刚性、明确、缺电子空腔的环四苯偶姻大环家族提供了非常有趣的结构单元。该大环对二氧化碳等线性客体分子表现出高亲和力，从而为亲二氧化碳持久性有机污染物的合成提供了理想的基础材料。在此，我们报道了在电离热条件下，使用低共熔氯化锌/氯化钠/氯化钾盐混合物，在 250 °C 下，通过环四苯偶酰和 1,2,4,5-四氨基苯之间的缩合反应合成了 POP。值得注意的是，在缩合反应之后，大环有利于三维（3D）生长，而不是二维生长，同时保留空腔。所得聚合物被命名为 3D-mPOP，具有高度微孔结构，BET 表面积为 1142 m2 g−1，具有高二氧化碳亲和力，结合焓为 39 kJ mol−1。此外，3D-mPOP 对二氧化碳/甲烷和二氧化碳/氮气混合物中的二氧化碳表现出非常高的选择性。
Abstract Porous organic polymers (POPs) incorporating macrocyclic units have been investigated in recent years in an effort to transfer macrocycles' intrinsic host–guest properties onto the porous networks to achieve complex separations. In this regard, highly interesting building blocks are presented by the family of cyclotetrabenzoin macrocycles with rigid, well-defined, electron-deficient cavities. This macrocycle shows high affinity towards linear guest molecules such as carbon dioxide, thus offering an ideal building block for the synthesis of CO2-philic POPs. Herein, we report the synthesis of a POP through the condensation reaction between cyclotetrabenzil and 1,2,4,5-tetraaminobenzene under ionothermal conditions using the eutectic zinc chloride/sodium chloride/potassium chloride salt mixture at 250 °C. Notably, following the condensation reaction, the macrocycle favors three-dimensional (3D) growth rather than a two-dimensional one while retaining the cavity. The resulting polymer, named 3D-mPOP, showed a highly microporous structure with a BET surface area of 1142 m2 g−1 and a high carbon dioxide affinity with a binding enthalpy of 39 kJ mol−1. Moreover, 3D-mPOP showed very high selectivity for carbon dioxide in carbon dioxide/methane and carbon dioxide/nitrogen mixtures.