Issue 22, 2014

Dehydration, dehydrogenation, and condensation of alcohols on supported oxide catalysts based on cyclic (WO3)3 and (MoO3)3 clusters

Abstract

Supported early transition metal oxides have important applications in numerous catalytic reactions. In this article, we review the synthesis and activity of well-defined model WO3 and MoO3 catalysts that are prepared via deposition of cyclic gas-phase (WO3)3 and (MoO3)3 clusters generated by sublimation of WO3 and MoO3 powders. Conversion of small aliphatic alcohols to alkenes, aldehydes/ketones, and ethers is employed to probe the structure–activity relationships on model catalysts ranging from unsupported (WO3)3 and (MoO3)3 clusters embedded in alcohol matrices, to (WO3)3 clusters supported on surfaces of other oxides, and epitaxial and nanoporous WO3 films. Detailed theoretical calculations reveal the underlying reaction mechanisms and provide insight into the origin of the differences in the WO3 and MoO3 reactivity. The catalytic activity for a range of interrogated (WO3)3 motifs (from unsupported clusters to nanoporous films) further sheds light onto the role structure and binding of (WO3)3 clusters with the support play in determining their catalytic activity.

Graphical abstract: Dehydration, dehydrogenation, and condensation of alcohols on supported oxide catalysts based on cyclic (WO3)3 and (MoO3)3 clusters

Article information

Article type
Review Article
Submitted
03 12 2013
First published
20 2 2014

Chem. Soc. Rev., 2014,43, 7664-7680

Author version available

Dehydration, dehydrogenation, and condensation of alcohols on supported oxide catalysts based on cyclic (WO3)3 and (MoO3)3 clusters

R. Rousseau, D. A. Dixon, B. D. Kay and Z. Dohnálek, Chem. Soc. Rev., 2014, 43, 7664 DOI: 10.1039/C3CS60445D

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