Direct Separation of High‐RON Gasoline From Six‐Component C ₅ ‐C ₆ Alkanes in a Sieving Metal–Organic Framework Adsorbent

Abstract The separation of six‐component C 5 ‐C 6 alkanes remains a critical challenge for high‐quality gasoline production due to their similar molecular sizes and properties. Herein, a gourd‐shaped Zn 4 (cpy‐2CH 3 ) 3 framework is developed featuring a strategically contracted aperture neck with a spacious cavity to selectively remove linear n‐C 5 and n‐C 6 alkane. The optimized architecture achieves exceptional molecular sieving performances, simultaneously achieving high adsorption capacities for linear n‐C 5 (2.88 mmol g −1 ) and n‐C 6 (2.47 mmol g −1 ) while completely excluding their branched and cyclic counterparts. Computational simulations elucidate the fundamental mechanism governing this selective adsorption behavior. Breakthrough experiments further confirm its superior practical separation feasibility with excellent cyclability, even under humid conditions. Moreover, Zn 4 (cpy‐2CH 3 ) 3 enables direct production of high research octane number (RON) (>90) gasoline from six‐component C 5 ‐C 6 alkane mixtures, which collectively establish Zn 4 (cpy‐2CH 3 ) 3 as a potent adsorbent for high‐RON gasoline production.