Atomistic Investigations of the Effects of Si/Al Ratio and Al Distribution on the Adsorption Selectivity of <i>n</i>-Alkanes in Brønsted-Acid Zeolites

The adsorption of &lt;em&gt;n&lt;/em&gt;-alkanes onto Brønsted-acid sites is a key step in the catalytic cracking of alkanes. Employing configurational-bias Monte Carlo simulations, we have investigated how the ratio of equilibrium adsorption constants for central C-C bonds relative to terminal bonds of &lt;em&gt;n&lt;/em&gt;-alkanes (i.e., the adsorption selectivity ratio) in Brønsted-acid zeolites is influenced by the Si/Al ratio and the Al distribution. A new computational approach was implemented, and the developed force field was validated by a comprehensive comparison between simulation results and experimental data for a number of Brønsted-acid zeolites. While the adsorption selectivity seems to be relatively insensitive to the Si/Al ratio, our results reveal that the Al distribution plays a crucial role in determining the adsorption selectivity. Changes in the Al distribution result in a change of as much as 2-fold in the adsorption selectivity ratio for &lt;em&gt;n&lt;/em&gt;-hexane. The selectivity generally shows larger variations with respect to Al distribution in zeolites with a larger Si/Al ratio. The two factors identified by this work that substantially influence the selectivity ratio are the siting of Al atoms among T-sites and their spatial proximity, and an atomic-level understanding of each of these effects was achieved. The siting of Al atoms at more or less selective T-sites significantly influences the overall selectivity ratio, and Al atoms in close proximity can synergistically enhance the adsorption of central C-C bonds, leading to a higher selectivity ratio relative to isolated Al atoms. Finally, we anticipate that these results will have important implications for future large-scale computational screenings and the development of advanced synthesis approaches to target certain Al distributions in zeolites.