Insights into adsorption of various gases on extra-framework cations of zeolite: A dispersion corrected DFT study on zeolite cluster models with Li +, Na + and K+ charge compensating ions

Design of an economical and sustainable gas separation material is relevant in several industrial processes. Zeolites with tunable pore sizes are ideal molecular sieves of many gases. The adsorption centers of these molecular sieves are extra-framework Lewis acid centers. In this study, we attempt to delineate the electronic properties of such centers ( Li+, Na+ and K+) and their sorption properties towards N2, O2, CO, CO2 and H2. Negative framework of zeolites are modeled using different cluster models that present distinct electronic environment and role of this environment on the Lewis acidity of the cation. The sorption property towards different gases is evaluated using dispersion corrected DFT studies. The results obtained are benchmarked for one of the studied model using CCSD calculations. The results indicate that while the local environment modulates the adsorption properties, the relative adsorption properties between different ions follow the same order irrespective of the type of negative framework modeled. This reveals that intrinsic atomic properties of the charge compensating cations drive the sorption properties of the zeolites. Adsorption energies compounded with the analysis of IR stretching frequencies of the adsorbed gases reveals that Li centers shows molecular adsorption (charge donation to the cationic centers) towards N2 as compared to O2 and towards CO2/CO as compared to H2, demonstrating the applicability of Li-Zeolites as ideal membranes for oxygen concentrators and syngas separation. These adsorption studies are ratified by the BOMD simulations at 300 K, where H2 and O2 desorbs while N2, CO and CO2 remains adsorbed to the cationic site. [Display omitted] •Adsorption of N2 over O2 and CO2/CO over H2 is understood from zeolite models.•Lithium based zeolite framework has best adsorption for N2, CO2 and CO.•BOMD simulations reveals that N2 binds to the cation while O2 gets desorbed.•CO2 and CO remains adsorbed and H2 gets desorbed from the zeolite framework.•At 330 K, N2 and CO gets desorbed while CO2 gets desorbed at 350 K.