A cage-based MOF displays excellent hydrolytic stability as well as promising potential for diverse gas separation applications.

Two NbO-type MOFs with N-oxide functionality immobilized in the pore surface display significantly enhanced C2H2/CH4 and CO2/CH4 separation performance.

The development of porous materials for ethylene (C2H4) separation and purification, a very important separation process in the chemical industry, is urgently needed but quite challenging. In particular, the realization of selectivity-reversed adsorption (namely, C2H4 is not preferentially adsorbed) and the simultaneous capture of multinary coexisting impurities such as ethane (C2H6) and acetylene (C2H2) will significantly simplify process design and reduce energy and cost consumption, but such porous materials are quite difficult to design and have not yet been fully explored. In this work, by employing an aromatic-rich bithiophene-based tetraisophthalate ligand, we solvothermally fabricated an anionic In­(III)-based framework termed ZJNU-115 featuring In­(COO)4 as an inorganic secondary building unit as well as one-dimensional channels. Due to the absence of unsaturated metallic sites, together with aromatic-rich channel surface decorated with abundant hydrogen-bonding acceptors of carboxylate oxygen and thiophene sulfur atoms, desolvated ZJNU-115 exhibited an unusual adsorption relationship with respect to C2 hydrocarbons, namely, simultaneous and preferable capture of C2H6 and C2H2 over C2H4 at the temperatures investigated, thus representing a rare metal–organic framework (MOF) with the promising potential for one-step adsorption-phase purification of C2H4 from a trinary C2 hydrocarbon mixture. Compared to a few of the MOFs reported for such an application, ZJNU-115 displayed simultaneously good adsorption selectivities of both C2H2 and C2H6 over C2H4. Furthermore, its separation potential can be postsynthetically tailored by substituting dimethylammonium (Me2NH2 +) counterions with tetraalkyl ammonium ions (NR4 +; R = Me, Et, or n-Pr). More importantly, ZJNU-115 was stable in various organic solvents as well as aqueous solutions with pH values ranging from 5 to 9, thus laying a solid foundation for its practical applications. The design principle and the performance regulation strategy adopted in this work will offer valuable guidance for the contrapuntal construction of porous MOFs employed for direct multicomponent purification of C2H4 with improved performance.