Fine‐Tuned Pore Architectures in Microporous Metal‐Organic Frameworks for Benchmark Storage and Purification of Fluorinated Propylene and Propane

ABSTRACT 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 C ₃ F ₆ and C ₃ F ₈ 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 C ₃ F ₆ and C ₃ F ₈ . Notably, the storage capacity and delivery efficiency of C ₃ F ₆ on functionalized Co‐MFU‐4L reach 219.7 cm ³ g ⁻¹ and 97%, respectively. Co‐MFU‐4 achieves a record C ₃ F ₈ productivity (purity >99.999%) of 3.3 L g ⁻¹ from 1/99 C ₃ F ₆ /C ₃ F ₈ 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.