Effect of cation reducibility on oxidative dehydrogenation of butane on orthovanadates

Ozie S. Owen, Harold H Kung

Research output: Contribution to journalArticle

61 Citations (Scopus)

Abstract

The orthovanadates of Mg, Zn, Cr, Ni, Cu and Fe were prepared, characterized with X-ray diffraction, laser Raman spectroscopy, and temperature programmed reduction, and tested for butane oxidation at 500°C using a feed of C4/O2/He of 4/8/88. The reaction results of these orthovanadates, when taken together with those of Nd, Sm and Eu orthovanadates obtained previously, indicated a correlation between the selectivity for oxidative dehydrogenation of butane to butenes and butadiene and the aqueous reduction potential of the component cation. The more reducible cations showed lower selectivities. The correlation was interpreted with a model that in the selectivity-determining step of the reaction, the probability that the surface intermediate could form a carbon-oxygen bond depended on the ease of removal of a lattice oxygen in the M-O-V group in the orthovanadate. Other correlations for the selectivity were attempted, which included the oxygen 1s binding energy and the electronegativity of the cations, but they were less successful.

Original languageEnglish
Pages (from-to)265-284
Number of pages20
JournalJournal of Molecular Catalysis
Volume79
Issue number1-3
DOIs
Publication statusPublished - Feb 15 1993

Fingerprint

Butane
Dehydrogenation
Positive ions
Oxygen
Electronegativity
Laser spectroscopy
Binding energy
Butadiene
Butenes
Raman spectroscopy
X ray diffraction
Oxidation
Carbon
Temperature

Keywords

  • butane
  • orthovanadates
  • oxidation (butane)
  • oxidative dehydrogenation

ASJC Scopus subject areas

  • Engineering(all)

Cite this

Effect of cation reducibility on oxidative dehydrogenation of butane on orthovanadates. / Owen, Ozie S.; Kung, Harold H.

In: Journal of Molecular Catalysis, Vol. 79, No. 1-3, 15.02.1993, p. 265-284.

Research output: Contribution to journalArticle

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AB - The orthovanadates of Mg, Zn, Cr, Ni, Cu and Fe were prepared, characterized with X-ray diffraction, laser Raman spectroscopy, and temperature programmed reduction, and tested for butane oxidation at 500°C using a feed of C4/O2/He of 4/8/88. The reaction results of these orthovanadates, when taken together with those of Nd, Sm and Eu orthovanadates obtained previously, indicated a correlation between the selectivity for oxidative dehydrogenation of butane to butenes and butadiene and the aqueous reduction potential of the component cation. The more reducible cations showed lower selectivities. The correlation was interpreted with a model that in the selectivity-determining step of the reaction, the probability that the surface intermediate could form a carbon-oxygen bond depended on the ease of removal of a lattice oxygen in the M-O-V group in the orthovanadate. Other correlations for the selectivity were attempted, which included the oxygen 1s binding energy and the electronegativity of the cations, but they were less successful.

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