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Atomic Layer Deposition of Vanadium Dioxide and a Temperature-dependent Optical Model
Published on: May 23, 2018
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Does Each Atom Count in the Reactivity of Vanadia Nanoclusters?
Mei-Qi Zhang1,2, Yan-Xia Zhao1, Qing-Yu Liu1,2
1Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, People's Republic of China.
Journal of the American Chemical Society
|December 13, 2016
Summary
Vanadium oxide clusters show size-dependent reactivity in hydrogen atom abstraction. Smaller clusters with specific oxygen deficiencies are highly reactive, while larger clusters exhibit bulk-like behavior, indicating a critical size of ~1.6 nm.
Area of Science:
- * Surface science and catalysis
- * Inorganic chemistry and materials science
- * Physical chemistry and reaction dynamics
Background:
- * Vanadium oxide clusters are investigated for their catalytic potential.
- * Understanding cluster size effects is crucial for designing efficient catalysts.
- * Oxygen deficiency in metal oxide clusters influences their reactivity.
Purpose of the Study:
- * To investigate the hydrogen atom abstraction (HAA) reactivity of vanadium oxide cluster anions with varying sizes and oxygen deficiencies.
- * To determine the critical size at which cluster behavior transitions to bulk behavior.
- * To elucidate the mechanism behind the observed reactivity trends.
Main Methods:
- * Preparation of vanadium oxide cluster anions [(V2O5)nVxOy−] using laser ablation.
- * Reaction of cluster anions with n-butane in a fast flow reactor.
- * Comparative study with scandium oxide clusters [(Sc2O3)nScxOy−].
Main Results:
- * For clusters smaller than ~1.6 nm (n < 25), Δ=1 oxygen-deficient clusters [(V2O5)nO−] exhibit significantly higher HAA reactivity.
- * For clusters larger than ~1.6 nm (n > 25), all five oxygen deficiency series show similar HAA reactivity.
- * Scandium oxide clusters consistently show higher HAA reactivity in the Δ=1 series across all sizes.
Conclusions:
- * A critical cluster size of approximately 1.6 nm (~V50O125) separates distinct size-dependent and bulk-like reactivity regimes.
- * The high reactivity of smaller Δ=1 vanadium oxide clusters is attributed to the presence of atomic oxygen radical anions (O•−).
- * Strong electron-phonon coupling in larger vanadia particles may facilitate O•− radical formation, explaining the shift in reactivity.
