Effects of cage topology on ethylene adsorption mechanism in silver exchanged CHA and RHO zeolites: An Inelastic Neutron Scattering and Density Functional study

Zeolite-based adsorbents have been successfully used for many challenging separations due to their tunable properties. A particularly notable application involves the separation of light olefins from paraffins, wherein the molecular sieving properties of zeolites play a pivotal role. Additionally, the selective interaction of alkenes with transition metal cations, positioned within the channels and cavities of microporous zeolites, further enhances separation capabilities. This study aims to comprehensively characterize the interactions between ethylene and Ag+ exchanged zeolites, employing a multidisciplinary approach, combining Inelastic Neutron Scattering (INS), Infrared (IR) spectroscopy, Nuclear Magnetic Resonance (NMR), UV–Vis and Density Functional Theory (DFT) calculations. CHA and RHO, zeolites largely applied in gas separation processes, were chosen due to their similar small pore sizes and pore volume, but different cavity shapes and flexibilities. The interpretation of derived DFT Electron Density Difference, experimentally supported by 13C Solid State NMR results, provide an understanding of each framework’s role during the charge transfer mechanisms between ethylene and transition metal species. Specific deformations in the flexible framework of zeolite RHO explain a blueshift of the band at 400 cm−1 in the librational region of INS spectra compared to CHA. This structural change in RHO, represented by the conic shape of the cage 8-ring side pockets, increases steric effects over the adsorbate while rendering the metallic adsorption center less exposed within the zeolite’s cavity, finally leading to a weaker adsorption energy. The redshift of C=C stretching frequencies observed by IR spectroscopy and DFT calculations, as well as C=C and C-H bond lengthening of ethylene confirm the formation of π-complexes on silver in both zeolites and allowed a further evaluation of the effects of the different frameworks cages on the aforementioned interaction. [Display omitted] •Ethylene forms a π complex with Ag+ species in Ag-zeolites as proved by INS and DFT.•The π complex is accommodated in the cages 8-ring side pockets.•CHA’s pocket is less constricted than deformed RHO’s pocket.•The denser electrostatic field around Ag+ in RHO leads to a weaker adsorption.•Framework geometry and flexibility play an important role in π complexation.