Density functional theory study of the oxidation of methanol to formaldehyde on a hydrated vanadia cluster
Impacto
Scholar |
Otros documentos de la autoría: González Navarrete, Patricio; Gracia, Lourdes; Calatayud Antonino, Mónica; Andres, Juan
Metadatos
Mostrar el registro completo del ítemcomunitat-uji-handle:10234/9
comunitat-uji-handle2:10234/7013
comunitat-uji-handle3:10234/8638
comunitat-uji-handle4:
INVESTIGACIONEste recurso está restringido
http://dx.doi.org/10.1002/jcc.21543 |
Metadatos
Título
Density functional theory study of the oxidation of methanol to formaldehyde on a hydrated vanadia clusterFecha de publicación
2010-10Editor
WileyISSN
0192-8651Cita bibliográfica
Journal of Computational Chemistry (2010), 31, 13, p. 2493-2501Tipo de documento
info:eu-repo/semantics/articleVersión de la editorial
http://onlinelibrary.wiley.com/doi/10.1002/jcc.21543/abstractVersión
info:eu-repo/semantics/publishedVersionPalabras clave / Materias
Resumen
Density functional theory was used to study the mechanism for the oxidation of methanol to formaldehyde. A vanadium oxide cluster O[DOUBLE BOND]V(OH)3 has been utilized to represent the catalytic system under hydrated ... [+]
Density functional theory was used to study the mechanism for the oxidation of methanol to formaldehyde. A vanadium oxide cluster O[DOUBLE BOND]V(OH)3 has been utilized to represent the catalytic system under hydrated conditions, i.e., in the presence of V[BOND]OH hydroxyl groups. Two types of methoxy-intermediates have been considered: a penta-coordinate methoxy-intermediate (OH)4V(OCH3) and a tetrahedral methoxy-intermediate (OH)2VO(OCH3)(H2O). The most plausible reaction pathway corresponds to the process involving first the formation of the tetrahedral methoxide, and a subsequent rate-limiting step where hydrogen is transferred from the methoxy groups toward the oxygen atom of the vanadyl V[DOUBLE BOND]O site. The reaction mechanism is a typical two-state reactivity process due to a change of the multiplicity (reactive singlet → product triplet) along the reaction coordinate accompanied by a reduction of the vanadium center from VV (d0) to VIII (d2). Minimum energy crossing points were localized and possible spin inversion processes are discussed by means of the intrinsic reaction coordinate approach to find the most favorable reaction pathways. The hydration effect is found to be mainly the destabilization of the methoxy intermediates. An alternative reaction pathway with a lower apparent barrier is presented [-]
Derechos de acceso
Copyright © 2010 Wiley Periodicals, Inc.
http://rightsstatements.org/vocab/InC/1.0/
info:eu-repo/semantics/closedAccess
http://rightsstatements.org/vocab/InC/1.0/
info:eu-repo/semantics/closedAccess
Aparece en las colecciones
- QFA_Articles [829]