Porous organic polymers (POPs) have a good potential for gas separation applications owing to their large surface area, structural robustness and chemical tunability. Previous studies have demonstrated the utility of POP-based adsorbents for carbon dioxide separation. However, no study has so far reported on the potential of POPs for capturing sulfur hexafluoride (SF₆), which is an extremely potent greenhouse gas. Here we demonstrate that the amine-incorporated POPs synthesized through the co-condensation of dichloroxylene (DCX) and triphenylamine (TPA) for application in SF₆/N₂ separation. Large surface area and pore volume of DCX-based POPs provide the structural framework for high SF₆ adsorption. The incorporation of tertiary amines favors the SF₆/N₂ selectivity without sacrificing the SF₆ adsorption at the point of interest (0.1 bar) according to the combined evaluations of the ideal adsorbed solution theory and idealized vacuum swing adsorption. Further analysis revealed that the tertiary amines increase the isosteric heat of adsorption, a measure of affinity between adsorbate and adsorbent. Undertaking a comparative adsorption kinetics study, we also demonstrated that TPA-containing POPs exhibit much faster SF₆ uptake than zeolite 13X, a commonly used commercial adsorbent, owing the co-existence of microporosity and mesoporosity that facilitates the diffusion of adsorbate within the adsorbent. Dynamic breakthrough and chromatographic measurements further confirmed the enhanced SF₆ adsorption kinetics of TPA-containing POPs. In overall, we attributed the high SF₆ separation performance of TPA-containing POPs to their two main characteristics: i) the presence of large micropores (c.a. 1.2 nm) alongside hierarchical mesoporosity, ii) the selectivity provided by amine functionalities.

多孔有机聚合物（POPs）由于具有较大的表面积，结构坚固性和化学可调性，因此在气体分离应用中具有良好的潜力。先前的研究表明，基于POP的吸附剂可用于二氧化碳分离。但是，到目前为止，尚未有关于持久性有机污染物捕获六氟化硫（SF ₆）的潜力的研究的报道。六氟化硫是一种非常有效的温室气体。在这里，我们证明了通过二氯二甲苯（DCX）和三苯胺（TPA）的共缩合反应合成的结合胺的POPs可以用于SF ₆ / N ₂分离。基于DCX的POP的大表面积和孔体积为高SF ₆提供了结构框架吸附。根据理想吸附溶液理论和理想真空变幅吸附的综合评估，叔胺的加入有利于SF ₆ / N ₂选择性，而不牺牲目标点（0.1 bar）的SF ₆吸附。进一步的分析表明，叔胺增加了吸附的等排热，这是被吸附物与吸附剂之间亲和力的量度。进行了比较吸附动力学研究，我们还证明了含有TPA的POPs表现出更快的SF ₆与沸石13X（一种常用的市售吸附剂）相比，它具有更高的吸收能力，因为微孔和中孔同时存在，可促进吸附剂在吸附剂中的扩散。动态突破和色谱测量结果进一步证实了含有TPA的POPs的SF ₆吸附动力学增强。总体而言，我们将含TPA的POPs的高SF ₆分离性能归因于其两个主要特征：i）除分级介孔外还存在大孔（ca 1.2 nm），ii）胺官能团提供的选择性。