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peer-reviewed, Selective separation of propyne/propadiene mixture to obtain pure propadiene (allene), an essential feedstock for organic synthesis, remains an unsolved challenge in the petrochemical industry, thanks mainly to their similar physicochemical properties. We herein introduce a convenient and energy-efficient physisorptive approach to achieve propyne/propadiene separation using microporous metal-organic frameworks (MOFs). Specifically, HKUST-1, one of the most widely studied high surface area MOFs that is available commercially, is found to exhibit benchmark performance (propadiene production up to 69.6 cm3/g, purity > 99.5%) as verified by dynamic breakthrough experiments. Experimental and modeling studies provide insight into the performance of HKUST-1 and indicate that it can be attributed to a synergy between thermodynamics and kinetics that arises from abundant open metal sites and cage-based molecular traps in HKUST-1.

peer-reviewed, Coordination networks that reversibly switch between closed and open phases are of topical interest since their stepped isotherms can offer higher working capacities for gas‐storage applications than the related rigid porous coordination networks. To be of practical utility, the pressures at which switching occurs, the gate‐opening and gate‐closing pressures, must lie between the storage and delivery pressures. Here we study the effect of linker substitution to fine‐tune gate‐opening and gate‐closing pressure. Specifically, three variants of a previously reported pcu‐topology MOF, X‐pcu‐5‐Zn, have been prepared: X‐pcu‐6‐Zn, 6=1,2‐bis(4‐pyridyl)ethane (bpe), X‐pcu‐7‐Zn, 7=1,2‐bis(4‐pyridyl)acetylene (bpa), and X‐pcu‐8‐Zn, 8=4,4′‐azopyridine (apy). Each exhibited switching isotherms but at different gate‐opening pressures. The N2, CO2, C2H2, and C2H4 adsorption isotherms consistently indicated that the most flexible dipyridyl organic linker, 6, afforded lower gate‐opening and gate‐closing pressures. This simple design principle enables a rational control of the switching behavior in adsorbent materials.