Tröger's Base Network Polymers of Intrinsic Microporosity (TB-PIMs) with Tunable Pore Size for Heterogeneous Catalysis.
Tröger's Base Network Polymers of Intrinsic Microporosity (TB-PIMs) with Tunable Pore Size for Heterogeneous Catalysis.
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DOI：
10.1021/jacs.2c04739
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发表时间：
2022-08-31
影响因子：
15
通讯作者：
Carta M
中科院分区：
文献类型：
--
作者：
Antonangelo AR;Hawkins N;Tocci E;Muzzi C;Fuoco A;Carta M
多相催化在高附加值化学品的制备中起着举足轻重的作用，当与多孔材料和载体结合时，它的工作效率更高。因此，在评价新型多相催化剂的性能时，对孔隙率和孔径进行详细的评估是必不可少的。在这里，我们报道了一系列具有可调孔径的新型微孔Tröger碱聚合物和共聚物(TB-PIM)的合成和表征。利用Tb中心的碱性催化苯甲醛和丙二腈的Knovenagel缩合反应，通过适当选择单体和共聚单体，可以系统地调节孔的大小。孔径的可调性为底物提供了更好的催化位置，从而大大提高了转化率，最好的结果只需20分钟就能完成。此外，它还可以使用大的苯甲醛，这在使用具有非常小的孔洞的聚合物时是不可能的，这是传统PIM的典型特征。催化反应比相应的均相反应效率更高，并最终通过添加少量溶剂进行优化，这有助于孔的膨胀，导致性能的进一步改善和更好的碳经济性。通过对共聚物结构的分子动力学模拟，描述了柔性链的溶胀性，有助于理解聚合物性能的改善，展示了这些新型材料的巨大潜力。
Heterogeneous catalysis plays a pivotal role in the preparation of value-added chemicals, and it works more efficiently when combined with porous materials and supports. Because of that, a detailed assessment of porosity and pore size is essential when evaluating the performance of new heterogeneous catalysts. Herein, we report the synthesis and characterization of a series of novel microporous Tröger’s base polymers and copolymers (TB-PIMs) with tunable pore size. The basicity of TB sites is exploited to catalyze the Knoevenagel condensation of benzaldehydes and malononitrile, and the dimension of the pores can be systematically adjusted with an appropriate selection of monomers and comonomers. The tunability of the pore size provides the enhanced accessibility of the catalytic sites for substrates, which leads to a great improvement in conversions, with the best results achieving completion in only 20 min. In addition, it enables the use of large benzaldehydes, which is prevented when using polymers with very small pores, typical of conventional PIMs. The catalytic reaction is more efficient than the corresponding homogeneous counterpart and is ultimately optimized with the addition of a small amount of a solvent, which facilitates the swelling of the pores and leads to a further improvement in the performance and to a better carbon economy. Molecular dynamic modeling of the copolymers’ structures is employed to describe the swellability of flexible chains, helping the understanding of the improved performance and demonstrating the great potential of these novel materials.
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