Details

Autor(en) / Beteiligte

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

Titel

Water reactivity with tungsten oxides: H2 production and kinetic traps

Ist Teil von

• The Journal of chemical physics, 2009-10, Vol.131 (14)

Erscheinungsjahr

2009

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• In a recent mass spectrometry/photoelectron spectroscopy study on the reactions between W2Oy− (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 W2O6H2−. 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 [W2Oy− (y=4–6)] and water. By calculating the free energy corrected reaction profiles, our results provide an explanation for the formation of W2O6H2−. We propose a mechanism in which water reacts with a metal oxide cluster and eliminates H2. The results from our calculations show that this is nearly a barrierless process for all suboxide clusters with the exception of W2O5−.