Structure-specific reactivity of alumina-supported monomeric vanadium oxide species

Hacksung Kim, Glen A. Ferguson, Lei Cheng, Stan A. Zygmunt, Peter C Stair, Larry A. Curtiss

Research output: Contribution to journalArticle

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Abstract

Oxidative dehydrogenation (ODH) catalysts based on vanadium oxide are active for the production of alkenes, chemicals of great commercial importance. The current industrial practice for alkene production is based on energy-intensive, dehydrogenation reactions. UV resonance and visible Raman measurements, combined with density functional studies, are used to study for the first time the structure-reactivity relationships for alumina-supported monomeric vanadium oxide species. The relationship between the structure of three vanadium oxide monomeric surface species on a θ-alumina surface, and their reducibility by H 2 was determined by following changes in the vanadias UV Raman and resonance Raman spectra after reaction with H 2 at temperatures from 450 to 650 °C. The H 2 reducibility sequence for the three monomeric species is bidentate > "molecular"> tridentate. The reaction pathways for H 2 reduction on the three vanadium oxide monomeric structures on a θ-alumina surface were investigated using density functional theory. Reduction by H 2 begins with reaction at the V=O bond in all three species. However, the activation energy, Gibbs free energy change under reaction conditions, and the final V oxidation state are species-dependent. The calculated ordering of reactivity is consistent with the observed experimental ordering and provides an explanation for the ordering. The results suggest that synthesis strategies can be devised to obtain vanadium oxide structures with greatly enhanced activity for ODH resulting in more efficient catalysts.

Original languageEnglish
Pages (from-to)2927-2932
Number of pages6
JournalJournal of Physical Chemistry C
Volume116
Issue number4
DOIs
Publication statusPublished - Feb 2 2012

Fingerprint

Vanadium
vanadium oxides
Aluminum Oxide
Oxides
Alumina
reactivity
aluminum oxides
Dehydrogenation
dehydrogenation
Alkenes
alkenes
Olefins
catalysts
Catalysts
Gibbs free energy
Density functional theory
Raman scattering
Activation energy
Raman spectra
activation energy

ASJC Scopus subject areas

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

Cite this

Structure-specific reactivity of alumina-supported monomeric vanadium oxide species. / Kim, Hacksung; Ferguson, Glen A.; Cheng, Lei; Zygmunt, Stan A.; Stair, Peter C; Curtiss, Larry A.

In: Journal of Physical Chemistry C, Vol. 116, No. 4, 02.02.2012, p. 2927-2932.

Research output: Contribution to journalArticle

Kim, Hacksung ; Ferguson, Glen A. ; Cheng, Lei ; Zygmunt, Stan A. ; Stair, Peter C ; Curtiss, Larry A. / Structure-specific reactivity of alumina-supported monomeric vanadium oxide species. In: Journal of Physical Chemistry C. 2012 ; Vol. 116, No. 4. pp. 2927-2932.
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