Efficient separation of methanol‐to‐olefins products with two novel amide‐functionalized Cu‐MOFs

Abstract Ethylene (C 2 H 4 ) and propylene (C 3 H 6 ), key products of the methanol‐to‐olefins (MTO) process, are vital chemical feedstocks. However, separating and purifying C 3 H 6 /C 2 H 4 mixtures remains highly challenging due to their similar physicochemical properties. Through the mixed‐ligand strategy with both N,N′‐bis(3,5‐dicarboxyphenyl)‐oxalamide (H 4 BDPO) and either 4,4′‐bipyridine (bpy) or di(pyridin‐4‐yl)amine (dpa), respectively, two novel amide‐functionalized MOFs, [Cu 6 (BDPO) 3 (bpy) 2 (H 2 O)]· x solvent (NJTU‐Bai85, NJTU‐Bai = Nanjing Tech University Bai’s group) and [Cu 6 (BDPO) 3 (dpa) 2 (H 2 O)]· x solvent (NJTU‐Bai86) were synthesized with high C 3 H 6 capacities (181 and 191 cm 3 g −1 at 298 K and 1 bar, respectively) and exceptional C 3 H 6 /C 2 H 4 selectivity (9.5 and 9.2, respectively), even at elevated temperatures. Furthermore, dynamic breakthrough experiments demonstrate that C 3 H 6 /C 2 H 4 mixture (50/50, 20/50, and 10/90, v / v ) can be effectively separated in one step and obtain polymer‐grade C 2 H 4 (≥ 99.5%) with ultra‐high productivity (137 and 133 L kg −1 , respectively) at 298 K and very interestingly, the MOF‐packed separation column shows markedly distinct retention times for C 2 H 4 and C 3 H 6 , highlighting their potential for industrial gas separation application.