Multifunctional Microporous Polymer Networks by Oxidative Polymerizations

微孔聚合物网络(MPN)是一种新兴的新型功能材料，它结合了沸石、活性碳或金属有机骨架等传统多孔材料的几个优点。由于扭曲但刚性的结构，这些聚合物表现出异常高的孔隙率，同时它们的共价有机性质确保了重量轻、热稳定性和化学稳定性高。由于仅由有机化合物组成，因此可以精确地控制大片可接近表面区域的化学性质以及由此产生的网络的物理性质。所有这些性质使得微孔聚合物在许多方面都有应用价值，特别是在气体储存和分离方面，但最近也显示了它们在能源应用或有机电子方面的巨大潜力。最后，MPN在催化领域开辟了新的前景，因为各种有机官能团可以被引入作为聚合物主链的维护部分。该项目将开发通过氧化聚合新的、功能性的噻吩咔唑或吡咯单体合成的MPN。我们将合成孔隙率、比表面积、微观结构和形态以及官能团分布良好的网络，并测试其气体吸附和电子性能。我们将首次通过精心选择的单体共聚制备多功能MPN，并将其应用于重要的反应，如光催化裂水和其他各种反应，在这些反应中，(对映体)选择性将通过生物启发的方法来定制，即在功能性有机环境中引入活性金属中心。

Microporous Polymer Networks (MPNs) are an emerging new class of functional materials, which combine several advantages of conventional porous matter, like zeolites, activated charcoals or metal¿organic frameworks. Due to a contorted but rigid structure, these polymers exhibit exceptionally high porosities, while their covalent organic nature ensures lightweight and high thermal and chemical stability. As solely composed of organic compounds, an exquisite control over the chemical nature of the large accessible surface areas as well as the physical properties of the resulting networks is possible. All these properties make microporous polymers interesting for a number of applications, especially for gas storage and separation, but recently also their great potential in energy applications or for organic electronics has been shown. Finally, MPNs open new prospects in the field of catalysis, as various organic functionalities can be introduced as maintaining parts of the polymer backbones. This project will develop MPNs synthesized by oxidative polymerization of novel, functional thiophene-, carbazole- or pyrrole- monomers. Networks with well-defined porosity, surface area, microstructure and morphology, as well as distribution of functional groups will be synthesized and tested for their gas sorption and electronic properties. For the first time, we will prepare multifunctional MPNs by co-polymerization of carefully chosen monomers and apply them as catalyst for important reactions such as photocatalytic water splitting and diverse other reactions in which the (enantio)selectivity will be tailored by a bio-inspired approach namely the introduction of active metal sites in functional organic environments.