Density functional theory study of the oxidation of methanol to formaldehyde on a hydrated vanadia cluster
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Other documents of the author: González Navarrete, Patricio; Gracia, Lourdes; Calatayud Antonino, Mónica; Andres, Juan
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Show full item recordcomunitat-uji-handle:10234/9
comunitat-uji-handle2:10234/7013
comunitat-uji-handle3:10234/8638
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http://dx.doi.org/10.1002/jcc.21543 |
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Title
Density functional theory study of the oxidation of methanol to formaldehyde on a hydrated vanadia clusterDate
2010-10Publisher
WileyISSN
0192-8651Bibliographic citation
Journal of Computational Chemistry (2010), 31, 13, p. 2493-2501Type
info:eu-repo/semantics/articlePublisher version
http://onlinelibrary.wiley.com/doi/10.1002/jcc.21543/abstractVersion
info:eu-repo/semantics/publishedVersionSubject
Abstract
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 [-]
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