Molecular Sieving Properties of Nanoporous Mixed-Linker ZIF-62: Associated Structural Changes upon Gas Adsorption Application

The evaluation of the flexibility in zeolitic imidazolate frameworks (ZIFs) has been very useful to understand their performance in gas adsorption and separation applications. Here, we have evaluated the adsorption properties of a nanoporous mixed-linker ZIF-62 using a combination of gas adsorption measurements, grand canonical Monte Carlo simulations, and synchrotron X-ray powder diffraction under operando conditions. While adsorption studies in nanoporous ZIF-62 at 77 K and atmospheric pressure predict a large O2/N2 separation ability, computational studies anticipate that the observed differences must be attributed to kinetic restrictions of N2 to access the internal porosity at cryogenic temperatures. Interestingly, upon a small increase in the adsorption temperature (90 K vs 77 K), both N2 and O2 are able to access the inner porous structure through the promotion of a phase transition (ca. 3.8% volume expansion) upon gas adsorption. This narrow phase (np) to expanded phase (ep) structural transition in ZIF-62 is completely suppressed above 150 K. Based on the excellent molecular sieve properties of nanoporous ZIF-62 for O2/N2 at cryogenic temperatures, we extended our study to the adsorption of linear and branched hydrocarbons. This study predicts the preferential adsorption of alkanes over alkenes in ZIF-62 for small hydrocarbons (C2), while in the case of C3 hydrocarbons and above, the adsorption process is mainly defined by kinetic restrictions. J.S.-A. acknowledges financial support from the MINECO (Projects MAT2016-80285-p and PID2019-108453GB-C21). The authors acknowledge ALBA for providing beamtime (Project No. 2019023264). Computational work was supported by the Cambridge High-Performance Computing Service, the Cambridge Service for Data-Driven Discovery (CSD3).