Bioinspired recognition in metal-organic frameworks enabling precise sieving separation of fluorinated propylene and propane mixtures.

The separation of fluorinated propane/propylene mixtures remains a major challenge in the electronics industry. Inspired by biological ion channels with negatively charged inner walls that allow selective transport of cations, we presented a series of formic acid-based metal-organic frameworks (MFA) featuring biomimetic multi-hydrogen confined cavities. These MFA materials, especially the cobalt formate (CoFA), exhibit specific recognition of hexafluoropropylene (C3F6) while facilitating size exclusion of perfluoropropane (C3F8). The dual-functional adsorbent offers multiple binding sites to realize intelligent selective recognition of C3F6, as supported by theoretical calculations and in situ spectroscopic experiments. Mixed-gas breakthrough experiments validate the capability of CoFA to produce high-purity (>5 N) C3F8 in a single step. Importantly, the stability and cost-effective scalable synthesis of CoFA underscore its extraordinary potential for industrial C3F6/C3F8 separations. This bioinspired molecular recognition approach opens new avenues for the efficient purification of fluorinated electronic specialty gases.

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

The electronics industry necessitates highly selective adsorption separation of hexafluoropropylene (C3F6) from perfluoropropane (C3F8), 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 C3F8/C3F6. Remarkably, the temperature-dependent adsorption behavior enhances the discrimination between the larger C3F8 and the smaller C3F6, resulting in unprecedented C3F6/C3F8 selectivity (over 10,000) compared to other well-known porous materials at an optimal temperature (298 K). Dynamic breakthrough experiments demonstrate that high-purity C3F8 (over 99.999%) could be obtained from a C3F6/C3F8 (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 C3F6/C3F8 separation. Single-crystal structural analysis of C3F6-loaded Ca-tcpb and theoretical calculations elucidate the host-guest interaction via multiple intermolecular interactions.