Adsorption of Cyclohexane in Pure Silica Zeolites: High-Throughput Computational Screening Validated by Experimental Data.

Adsorption of cyclohexane in pure silica zeolites was studied experimentally and by molecular simulations. Based on the adsorption isobars obtained from the quasi-equilibrated temperature adsorption and desorption (QE-TPDA) measurements and reported adsorption isotherms for high-silica zeolites Y, ZSM-5, and ZSM-11 we refined Lennard-Jones parameters for guest-host interactions available in the literature. Adsorption of cyclohexane from equimolar mixture of twisted-boat and chair conformations has been screened in 171 pure silica zeolitic structures using grand canonical Monte Carlo simulations. Almost 20 frameworks showing extraordinary preference for adsorption of the chair conformation over the twisted boat one or vice versa were found. This selectivity was attributed to the geometry of channels and cavities present in the pore structures, as all t-boat selective structures possess channels or cavities of 8.3-9.1 Å. We also differentiated ways of chair-selectivity depending on the size and shape of the channels or cavities and also on the arrangement of the guest molecules in the pores.