Water reactivity with tungsten oxides

H 2 production and kinetic traps

Nicholas J. Mayhall, David W. Rothgeb, Ekram Hossain, Caroline Chick Jarrold, Krishnan Raghavachari

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

In a recent mass spectrometry/photoelectron spectroscopy study on the reactions between W 2 O y - (y=2-6) and water, Jarrold and co-workers [J. Chem. Phys. 130, 124314 (2009)] observed interesting differences in the reactivity of the different cluster ions. Particularly noteworthy is the observation that the only product with the incorporation of hydrogens is a single peak corresponding to W 2 O 6 H 2 -. As reactions between metal oxide clusters and small molecules such as water have high potential for catalytic applications, we carried out a careful study to obtain a mechanistic understanding of this observed reactivity. Using electronic structure calculations, we identified and characterized multiple modes of reactivity between unsaturated tungsten oxide clusters [W 2 O y - (y=4-6)] and water. By calculating the free energy corrected reaction profiles, our results provide an explanation for the formation of W 2 O 6 H 2 -. We propose a mechanism in which water reacts with a metal oxide cluster and eliminates H 2. The results from our calculations show that this is nearly a barrierless process for all suboxide clusters with the exception of W 2 O 5 -.

Original languageEnglish (US)
Article number144302
JournalJournal of Chemical Physics
Volume131
Issue number14
DOIs
StatePublished - 2009
Externally publishedYes

Fingerprint

tungsten oxides
reactivity
traps
Kinetics
Water
kinetics
Oxides
water
Metals
metal oxides
Photoelectron spectroscopy
Free energy
Electronic structure
Mass spectrometry
Hydrogen
Ions
mass spectroscopy
Molecules
free energy
tungsten oxide

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Mayhall, N. J., Rothgeb, D. W., Hossain, E., Jarrold, C. C., & Raghavachari, K. (2009). Water reactivity with tungsten oxides: H 2 production and kinetic traps. Journal of Chemical Physics, 131(14), [144302]. https://doi.org/10.1063/1.3242294

Water reactivity with tungsten oxides : H 2 production and kinetic traps. / Mayhall, Nicholas J.; Rothgeb, David W.; Hossain, Ekram; Jarrold, Caroline Chick; Raghavachari, Krishnan.

In: Journal of Chemical Physics, Vol. 131, No. 14, 144302, 2009.

Research output: Contribution to journalArticle

Mayhall, NJ, Rothgeb, DW, Hossain, E, Jarrold, CC & Raghavachari, K 2009, 'Water reactivity with tungsten oxides: H 2 production and kinetic traps', Journal of Chemical Physics, vol. 131, no. 14, 144302. https://doi.org/10.1063/1.3242294
Mayhall NJ, Rothgeb DW, Hossain E, Jarrold CC, Raghavachari K. Water reactivity with tungsten oxides: H 2 production and kinetic traps. Journal of Chemical Physics. 2009;131(14). 144302. https://doi.org/10.1063/1.3242294
Mayhall, Nicholas J. ; Rothgeb, David W. ; Hossain, Ekram ; Jarrold, Caroline Chick ; Raghavachari, Krishnan. / Water reactivity with tungsten oxides : H 2 production and kinetic traps. In: Journal of Chemical Physics. 2009 ; Vol. 131, No. 14.
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