Yang C.-T.Janda A.Bell A.T.Lin L.-C.LI-CHIANG LIN2022-05-242022-05-242018https://www.scopus.com/inward/record.uri?eid=2-s2.0-85046644088&doi=10.1021%2facs.jpcc.7b11190&partnerID=40&md5=dfae5a06459636a20e6fd62a1871b77ehttps://scholars.lib.ntu.edu.tw/handle/123456789/611482The adsorption of n-alkanes onto Br?nsted-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 n-alkanes (i.e., the adsorption selectivity ratio) in Br?nsted-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 Br?nsted-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 n-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. 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. ? 2018 American Chemical Society.AdsorptionAtomsCatalytic crackingEquilibrium constantsHexaneIntelligent systemsMonte Carlo methodsParaffinsZeolitesAdsorption selectivityComprehensive comparisonsComputational approachConfigurational-bias monte carloEquilibrium adsorption constantImplications for futuresSelectivity ratioSpatial proximityAluminumjournal article10.1021/acs.jpcc.7b111902-s2.0-85046644088