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

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 beta-hydrogen transfer to a terminal M-O. Dehydrogenation takes place via an alpha-hydrogen transfer to an adjacent Mo-VI=O atom or a W-VI 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. The Lewis acidity of the metal center with W-VI being larger than Mo-VI results in the increased reactivity of W3O9 over Mo3O9 for dehydrogenation and dehydration. However, the product selection of aldehyde or ketone and olefin is determined by the reducibility of the metal center. Our calculations are consistent with the experiment in terms of the dehydrogenation, dehydration, and H/D exchange reactions. The condensation reaction requires a third alcohol with the sacrifice of an alcohol to form a metal hydroalkoxide, a strong gas-phase Bronsted acid. This Bronsted acid-driven reaction is different from the dehydrogenation and dehydration reactions that are governed by the Lewis acidity of the metal center.