Leveraging Surface Polarity in a Cost‐Effective Metal–Organic Framework for Olefin Purification From Methanol‐to‐Olefin Products

Abstract Research over the years has revealed the immense potential of metal–organic frameworks (MOFs) for purifying olefins such as ethylene (C 2 H 4 ) and propylene (C 3 H 6 ). However, many of these MOFs face challenges in terms of economic viability, particularly in production scalability, long‐term stability, and process capability. In this study, we present a low‐cost and easily scalable synthesis of a robust MOF material (JNU‐74a), featuring a balanced surface polarity that allows for one‐step C 2 H 4 and C 3 H 6 purification from methanol‐to‐olefin (MTO) products. By incorporating highly electronegative atoms on the nonpolar surface, JNU‐74a exhibits substantially larger absorption capacity and stronger binding affinity for C 3 H 6 and ethane (C 2 H 6 ) compared to C 2 H 4 , as evidenced by their gas adsorption isotherms and heats of adsorption measurements. In‐depth analyses through in situ single‐crystal X‐ray diffraction (SCXRD) of gas@JNU‐74a unveil multiple supramolecular bindings that favor C 3 H 6 and C 2 H 6 , confirming their preferential adsorption over C 2 H 4 . Breakthrough experiments demonstrate that JNU‐74a can efficiently produce polymer‐grade C 2 H 4 (≥99.95%) and C 3 H 6 (≥99.5%) from C 2 H 6 /C 2 H 4 , C 3 H 6 /C 2 H 4 , and C 3 H 6 /C 2 H 6 /C 2 H 4 mixtures of different ratios in a single adsorption‐desorption cycle. With its impressive separation capability, high chemical stability, and cost‐effective production, JNU‐74a holds promise for olefin purification from MTO products and other challenging industrial separations.