Fine-Tuned Pore Architectures in Microporous Metal-Organic Frameworks for Benchmark Storage and Purification of...

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.