Scalable Synthesis of Robust MOF for Challenging Ethylene Purification and Propylene Recovery with Record Productivity

Abstract Ethylene (C 2 H 4 ) purification and propylene (C 3 H 6 ) recovery are highly relevant in polymer synthesis, yet developing physisorbents for these industrial separation faces the challenges of merging easy scalability, economic feasibility, high moisture stability with great separation efficiency. Herein, we reported a robust and scalable MOF (MAC‐4) for simultaneous recovery of C 3 H 6 and C 2 H 4 . Through creating nonpolar pores decorated by accessible N/O sites, MAC‐4 displays top‐tier uptakes and selectivities for C 2 H 6 and C 3 H 6 over C 2 H 4 at ambient conditions. Molecular modelling combined with infrared spectroscopy revealed that C 2 H 6 and C 3 H 6 molecules were trapped in the framework with stronger contacts relative to C 2 H 4 . Breakthrough experiments demonstrated exceptional separation performance for binary C 2 H 6 /C 2 H 4 and C 3 H 6 /C 2 H 4 as well as ternary C 3 H 6 /C 2 H 6 /C 2 H 4 mixtures, simultaneously affording record productivities of 27.4 and 36.2 L kg −1 for high‐purity C 2 H 4 (≥99.9 %) and C 3 H 6 (≥99.5 %). MAC‐4 was facilely prepared at deckgram‐scale under reflux condition within 3 hours, making it as a smart MOF to address challenging gas separations.