Leveraging Surface Chemistry and Pore Shape Engineering in a Metal‐Organic Framework for One‐Step Olefin Purification

Abstract Purifying olefin from ternary paraffin/olefin/alkyne mixtures through a one‐step adsorption process is extremely desirable. Herein, a stable zirconium(IV) metal‐organic framework with a customized pore surface composed of nonpolar phenyl and slightly polar thiophene rings is reported to access the adsorption preference of paraffin and alkyne over olefin. Noteworthily, this material displays a superior ability to discriminate C₃ hydrocarbon molecules, which is principally more challenging compared with C₂ ones and rarely documented. Computational studies disclose that its featured pore shape fits well with C₃ gas molecules, enabling them to get close contact with the immobilized affinity sites. Leveraging surface chemistry and pore shape engineering synergistically gives rise to excellent C₃ adsorption capacities (>5 mmol g⁻¹) and concurrently high C₃H₈/C₃H₆ (1.4) and C₃H₄/C₃H₆ (1.9) selectivities (at 298 K and 1 atm). Dynamic column breakthrough experiments demonstrate that one‐step purification of C₂H₄ and C₃H₆ can be simultaneously realized on this material.