The high fractional free volume (FFV) endowed polymers of intrinsic microporosity (PIMs) with high gas permeability but low selectivity. Herein, an intermediate temperature range was deliberately utilized to tune PIM‐1 membrane microstructure in nitrogen atmosphere to enhance gas separation performance. During intermediate thermal manipulation, the synergistic effects of thermal‐induced cross‐linking and decomposition on PIM‐1 membranes have optimized the micropores for significantly increasing membrane molecular‐sieving ability with the boosted selectivity of 350 (H₂/N₂), 1,472 (H₂/CH₄), 3,774 (H₂/C₃H₈), and 197 (CO₂/CH₄) respectively, with the H₂ permeability of 234 Barrer, correspondingly, surpassing the “Robeson's Upper Bound”. The facile strategy simultaneously utilizing the thermal‐induced cross‐linking and decomposition, might provide a new platform to develop the high‐performance membranes for highly‐efficient hydrogen purification and CO₂ separations.

中文翻译：

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用于气体分离的本征微孔（PIM）膜聚合物的中间热操作

高分数自由体积（FFV）赋予聚合物固有的微孔性（PIM），具有高的气体渗透性但选择性低。在此，故意在氮气氛中利用中间温度范围来调节PIM-1膜的微观结构，以增强气体分离性能。在中间热操作过程中，热诱导的交联和分解对PIM-1膜的协同作用优化了微孔，从而显着提高了膜分子筛分离能力，选择性提高了350（H ₂ / N ₂），1,472（ H ₂ / CH ₄），3,774（H ₂ / C ₃ H ₈）和197（CO ₂ / CH₄）分别具有234 Barrer的H ₂渗透率，超过了“ Robeson的上限”。同时利用热诱导的交联和分解的简便策略可能为开发用于高效氢纯化和CO ₂分离的高性能膜提供一个新平台。