Temperature-Responsive Molecular Sieving of Fluorinated Propylene and Propane via a Flexible Metal–Organic Framework with High-Density Open Metal Sites
Liangzheng Sheng, Wei Xia, Yue Fu, Jia‐Lei Yan, Zhijie Zhou, Zheng Fang, Fuxing Shen, Lihang Chen, Zhiguo Zhang, Qiwei Yang, Qilong Ren, Zongbi Bao
Abstract
The development of porous materials capable of achieving efficient separation of hexafluoropropylene (C 3 F 6 ) and octafluoropropane (C 3 F 8 ) remains a challenge due to their nearly identical physical properties and stringent purity demands in industrial applications. Herein, we report a flexible, quasi-one-dimensional coordination polymer, Mn-dhbq ([Mn(dhbq)(H 2 O) 2 ] n, where dhbq = 2,5-dihydroxy-1,4-benzoquinone), featuring a high density of open metal sites and a temperature-responsive swelling architecture. This unique combination enables dynamic molecular sieving through selective binding of C 3 F 6 while effectively excluding C 3 F 8 . At 298 K, dynamic breakthrough experiments with a 10:90 (v/v) C 3 F 6 /C 3 F 8 gas mixture yielded high-purity C 3 F 8 (≥99.999%) over 190 L/kg. Mn-dhbq demonstrated remarkable thermal, chemical, and hydrothermal stability, along with scalability for 100-gram-scale synthesis and moldability into industrially relevant pellets using organic binders. The combination of high stability, scalability, and temperature-responsive selectivity highlights Mn-dhbq as a promising candidate for energy-efficient separation of fluorinated gases, addressing critical purification challenges in the semiconductor and electronics industries.