DFT - Quantum chemical study of the HZSM-5-cyclohexene interaction pathways
Por:
Cuán A., Martínez-Magadán J.M., García-Cruz I., Galván M.
Publicada:
1 ene 2005
Resumen:
A theoretical analysis of the interaction between cyclohexene and a HZSM-5 zeolite model system is presented. Two different models were used to represent this catalyst: a ring structure model consisting of 10 TO4 tetrahedral sites (where T = Si, Al) and a smaller model containing 3 TO 4 tetrahedral sites. Two different reaction pathways were studied: the hydrogen exchange between the HZSM-5 cluster model and the cyclohexene molecule, and the proton addition to double bond of the cyclohexene. The alkoxy species can be stabilized/destabilized depending of the arrangement restriction between the olefin and the local geometry of the active site. When cyclohexene molecule interacts with the 3T model the reaction involves an alkoxy species formation. Due to the allowed relaxation in the ring framework around the active site, the local arrangement restriction of the alkoxy species and therefore the covalent alkoxy bond is too weak giving rise to a more ionic intermediate species (carbenium ion-like), which is characterized as a minimum in the PES. By using the non-interacting system, as a reference, and based on the calculated changes in the total energy of the different complexes, one is able to determine that both carbenium ion-like and alkoxy species are destabilized with respect to physisorbed complexes. © 2005 Elsevier B.V. All rights reserved.
Filiaciones:
Cuán A.:
Programa de Ingeniería Molecular, Instituto Mexicano del Petróleo, Eje Lazaro Cardenas 152, México 07730, D.F., Mexico
Departamento de Química, División de Ciencias Básicas e Ingeniería, Universidad Autónoma Metropolitana-Iztapalapa, A.P. 55-534, México 09340, D.F., Mexico
Martínez-Magadán J.M.:
Programa de Ingeniería Molecular, Instituto Mexicano del Petróleo, Eje Lazaro Cardenas 152, México 07730, D.F., Mexico
García-Cruz I.:
Programa de Ingeniería Molecular, Instituto Mexicano del Petróleo, Eje Lazaro Cardenas 152, México 07730, D.F., Mexico
Galván M.:
Departamento de Química, División de Ciencias Básicas e Ingeniería, Universidad Autónoma Metropolitana-Iztapalapa, A.P. 55-534, México 09340, D.F., Mexico
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