title: Structures and reaction mechanisms of cumene formation via benzene alkylation with propylene in a newly synthesized ITQ-24 zeolite: an embedded ONIOM study.
abstract: The cumene formation via benzene alkylation with propylene on the new three-dimensional nanoporous catalyst, ITQ-24 zeolite, has been investigated by using the ONIOM2(B3LYP/6-31G(d,p):UFF) method. Both consecutive and associative reaction pathways are examined. The contributions of the short-range van der Waals interactions, which are explicitly included in the ONIOM2 model, and an additional long-range electrostatic potential from the extended zeolite framework to the energy profile are taken into consideration. It is found that benzene alkylation with propylene in the ITQ-24 zeolite prefers to occur through the consecutive reaction mechanism. The benzene alkylation step is the reaction rate-determining step with an estimated activation energy of 35.70 kcal/mol, comparable with an experimental report in beta-zeolite of 34.9 kcal/mol. The electrostatic potential from the extended zeolite framework shows a much more significant contribution to the transition state selectivity than the van der Waals interactions.
authors.affiliation: Laboratory for Computational and Applied Chemistry, Department of Chemistry, Faculty of Science, Kasetsart University, Bangkok 10900, Thailand.
authors.forename: Bavornpon
authors.initials: B
authors.lastname: Jansang
authors.forename: Tanin
authors.initials: T
authors.lastname: Nanok
authors.forename: Jumras
authors.initials: J
authors.lastname: Limtrakul