Competitive oxidation and reduction of aliphatic alcohols over (wo3)3 clusters

Yu Kwon Kim, Z. Dohnálek, Bruce D. Kay, Roger Rousseau

Research output: Contribution to journalArticle

35 Citations (Scopus)

Abstract

The reactions of C1-C4 aliphatic alcohols over (WO 3) 3 clusters were studied experimentally and theoretically using temperature-programmed desorption, infrared reflection-absorption spectroscopy, and density functional theory. The results reveal that all C1-C4 aliphatic alcohols readily react with (WO 3) 3 clusters by heterolytic cleavage of the RO-H bond to give alkoxy (RO-) bound to W(VI) centers and a proton (H +) attached to the terminal oxygen atom of a tungstyl group (WdO). Two protons adsorbed onto the cluster readily react with the doubly bonded oxygen to from a water molecule that desorbs at 200-300 K and the alkoxy that undergoes decomposition at higher temperatures into the corresponding alkene, aldehyde, and/or ether. Our theory predicts that all three channels proceed over the W(VI) Lewis acid sites with energy barriers of 30-40 kcal/mol, where dehydration is favored over the others. We also present further analysis of the yield and reaction temperature as a function of the alkyl substituents and discuss the origin of the reaction selectivity among the three reaction channels.

Original languageEnglish
Pages (from-to)9721-9730
Number of pages10
JournalJournal of Physical Chemistry C
Volume113
Issue number22
DOIs
Publication statusPublished - Jun 4 2009

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Protons
alcohols
Alcohols
Oxygen
Lewis Acids
Oxidation
oxidation
Energy barriers
Alkenes
Temperature programmed desorption
Aldehydes
Dehydration
Absorption spectroscopy
Ether
Olefins
Density functional theory
Ethers
Infrared radiation
Decomposition
Atoms

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Competitive oxidation and reduction of aliphatic alcohols over (wo3)3 clusters. / Kim, Yu Kwon; Dohnálek, Z.; Kay, Bruce D.; Rousseau, Roger.

In: Journal of Physical Chemistry C, Vol. 113, No. 22, 04.06.2009, p. 9721-9730.

Research output: Contribution to journalArticle

Kim, Yu Kwon ; Dohnálek, Z. ; Kay, Bruce D. ; Rousseau, Roger. / Competitive oxidation and reduction of aliphatic alcohols over (wo3)3 clusters. In: Journal of Physical Chemistry C. 2009 ; Vol. 113, No. 22. pp. 9721-9730.
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