Temperature-dependent rearrangement of gas molecules in ultramicroporous materials for tunable adsorption of CO2 and C2H2.

The interactions between adsorbed gas molecules within porous metal-organic frameworks are crucial to gas selectivity but remain poorly explored. Here, we report the modulation of packing geometries of CO₂ and C₂H₂ clusters within the ultramicroporous CUK-1 material as a function of temperature. In-situ synchrotron X-ray diffraction reveals a unique temperature-dependent reversal of CO₂ and C₂H₂ adsorption affinities on CUK-1, which is validated by gas sorption and dynamic breakthrough experiments, affording high-purity C₂H₂ (99.95%) from the equimolar mixture of C₂H₂/CO₂ via a one-step purification process. At low temperatures (<253 K), CUK-1 preferentially adsorbs CO₂ with both high selectivity (>10) and capacity (170 cm³ g⁻¹) owing to the formation of CO₂ tetramers that simultaneously maximize the guest-guest and host-guest interactions. At room temperature, conventionally selective adsorption of C₂H₂ is observed. The selectivity reversal, structural robustness, and facile regeneration of CUK-1 suggest its potential for producing high-purity C₂H₂ by temperature-swing sorption. Guest clusters within confined nanospaces have a significant impact on molecular recognition. Here authors highlight the potential to systematically control gas-cluster rearrangement, leading to tunable sorption and separation behaviour in a MOF. [ABSTRACT FROM AUTHOR]