The oxidative dehydrogenation (ODH) of ethane on alumina-supported vanadia was investigated with the aim of understanding the effects of lattice oxygen and vanadium oxidation state on the catalyst ODH activity and ethene selectivity. Transient-response experiments were carried out with both a fully oxidized sample of 10 wt% VO(x)/Al(2)O(3) (7 V nm(-2)) and a sample that had been partially reduced in H(2). The experimental results were analyzed to determine the rate coefficients for ethane ODH, k(1), and ethene combustion, k(3). The rate of ODH was found to depend solely on the concentration of reactive oxygen in the catalyst, but not on the means by which this oxygen concentration was attained (i.e., by H(2)versus C(2)H(6) reduction). On the other hand, the ethene selectivity observed at a given concentration of active oxygen was found to depend on the composition of the reducing agent, higher ethene selectivities being observed when H(2), rather than C(2)H(6), was used as the reducing agent. It is proposed that the higher ethene selectivity achieved by H(2)versus C(2)H(6) reduction might be due to a lower ratio of V(4+) to V(3+) cations attained upon reduction in H(2) for a given extent of V(5+) reduction. This interpretation is based on the hypothesis that ethene combustion is initiated by C(2)H(4) adsorption on V(n+) cations present at the catalyst surface and that the strength of adsorption decreases in the order V(5+) > V(4+) > V(3+) consistent with the decreasing Lewis acidity of the cations.
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