Efficient Storage, delivery, and production of high-purity fluorinated specialty gases remain critical challenges in the semiconductor industry, where gas management directly determines the economic structure and competitiveness of chip manufacturing. Here, we report sub-angstrom pore-architecture engineering in microporous metal-organic frameworks, enabling highly efficient storage and purification of C3F6 and C3F8 at benchmark levels. By systematically tailoring linker length and terminal functional groups with sub-angstrom precision, a series of Co-based MFU-4-type materials were developed with progressively contracted pore apertures and distinct adsorption behaviors - from co-adsorption with ultrahigh storage capacity and delivery efficiency in Co-MFU-4L, to molecular size sieving in Co-MFU-4, and finally kinetic discrimination in Co-MFU-4-F for C3F6 and C3F8. Notably, the storage capacity and delivery efficiency of C3F6 on functionalized Co-MFU-4L reach 219.7 cm3 g-1 and 97%, respectively. Co-MFU-4 achieves a record C3F8 productivity (purity >99.999%) of 3.3 L g-1 from 1/99 C3F6/C3F8 mixture, as confirmed by dynamic breakthrough experiments. Molecular simulations and in situ Fourier transform infrared spectroscopy provide direct insights into the host-guest interactions. Precise pore-architecture tuning not only offers fundamental insights into the structure-property relationships at the sub-angstrom level but also demonstrates a promising route toward addressing challenges in "easy-on/off" delivery and purification of specialty gases.
Hui et al. (Tue,) studied this question.