Oxidation, Reduction, and Condensation of Alcohols over (MO3)3 (M = Mo, W) Nanoclusters

Autor:	Zongtang Fang, David A. Dixon, Zhenjun Li, Shenggang Li, Bruce D. Kay, Jamie M. Hennigan, Roger Rousseau, Matthew S. Kelley, Zdenek Dohnálek
Rok vydání:	2014
Předmět:	Olefin fiber Alcohol Photochemistry Redox Surfaces Coatings and Films Electronic Optical and Magnetic Materials Nanoclusters chemistry.chemical_compound General Energy chemistry Desorption Density functional theory Dehydrogenation Deuterated methanol Physical and Theoretical Chemistry
Zdroj:	The Journal of Physical Chemistry C. 118:22620-22634
ISSN:	1932-7455 1932-7447
DOI:	10.1021/jp5072132
Popis:	The reactions of deuterated methanol, ethanol, 1-propanol, 1-butanol, 2-propanol, 2-butanol, and tert-butanol over cyclic (MO3)3 (M = Mo, W) clusters were studied experimentally with temperature-programmed desorption and theoretically with coupled cluster CCSD(T) theory and density functional theory. The reactions of two alcohols per M3O9 cluster are required to provide agreement with experiment for D2O release, dehydrogenation, and dehydration. The reaction begins with the elimination of water by proton transfers and forms an intermediate dialkoxy species that can undergo further reaction. Dehydration proceeds by a β-hydrogen transfer to a terminal M═O. Dehydrogenation takes place via an α-hydrogen transfer to an adjacent MoVI═O atom or a WVI metal center with redox involved for M = Mo and no redox for M = W. The two channels have comparable activation energies. H/D exchange to produce alcohols can take place after olefin is released or via the dialkoxy species, depending on the alcohol and the cluster. ...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::a72c3a63a07901d800e1e8a3d2042766 https://doi.org/10.1021/jp5072132 Zobrazit plný text záznamu