Temperature-dependent molecular sieving of fluorinated propane/propylene mixtures by a flexible-robust metal-organic framework.

Xia, Wei; Yang, Yisi; Sheng, Liangzheng; Zhou, Zhijie; Chen, Lihang; Zhang, Zhangjing; Zhang, Zhiguo; Yang, Qiwei et al. · Sci Adv · 2024

basic_science · Level V

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Abstract

The electronics industry necessitates highly selective adsorption separation of hexafluoropropylene (C<sub>3</sub>F<sub>6</sub>) from perfluoropropane (C<sub>3</sub>F<sub>8</sub>), which poses a challenge due to their similar physiochemical properties. In this work, we present a microporous flexible-robust metal-organic framework (Ca-tcpb) with thermoregulatory gate opening, a rare phenomenon that allows tunable sieving of C<sub>3</sub>F<sub>8</sub>/C<sub>3</sub>F<sub>6</sub>. Remarkably, the temperature-dependent adsorption behavior enhances the discrimination between the larger C<sub>3</sub>F<sub>8</sub> and the smaller C<sub>3</sub>F<sub>6</sub>, resulting in unprecedented C<sub>3</sub>F<sub>6</sub>/C<sub>3</sub>F<sub>8</sub> selectivity (over 10,000) compared to other well-known porous materials at an optimal temperature (298 K). Dynamic breakthrough experiments demonstrate that high-purity C<sub>3</sub>F<sub>8</sub> (over 99.999%) could be obtained from a C<sub>3</sub>F<sub>6</sub>/C<sub>3</sub>F<sub>8</sub> (10:90) mixture under ambient conditions. The unique attributes of this material encompass exceptional adsorption selectivity, remarkable structural stability, and outstanding separation performance, positioning it as a highly promising candidate for C<sub>3</sub>F<sub>6</sub>/C<sub>3</sub>F<sub>8</sub> separation. Single-crystal structural analysis of C<sub>3</sub>F<sub>6</sub>-loaded Ca-tcpb and theoretical calculations elucidate the host-guest interaction via multiple intermolecular interactions.