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

Journal Article · Thu Oct 02 04:00:00 EDT 2014 · Journal of Physical Chemistry C, 118(39):22620-22634

DOI:https://doi.org/10.1021/jp5072132· OSTI ID:1164964

Fang, Zongtang; Li, Zhenjun; Kelley, Matthew S.; Kay, Bruce D.; Li, Shenggang; Hennigan, Jamie M.; Rousseau, Roger J.; Dohnalek, Zdenek; Dixon, David A.

The reactions of deuterated methanol, ethanol, 1-propanol, 1-butanol, 2-propanol, 2-butanol and t-butanol over cyclic (MO3)3 (M = Mo, W) clusters were studied experimentally with temperature programmed desorption (TPD) 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 which 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. The Lewis acidity of the metal center with WVI being larger than MoVI results in the increased reactivity of W3O9 over Mo3O9 for dehydrogenation and dehydration.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1164964
• Report Number(s): PNNL-SA-103803; 33194; KC0302010
• Journal Information: Journal of Physical Chemistry C, 118(39):22620-22634, Journal Name: Journal of Physical Chemistry C, 118(39):22620-22634
• Country of Publication: United States
• Language: English

Related Subjects

Environmental Molecular Sciences Laboratory