gamma-Al2O3-supported vanadium oxide catalysts (0-6.3 wt% V atoms) wer
e prepared, characterized, and tested for the oxidative dehydrogenatio
n (ODH) of both ethane and n-butane. The vanadium loading strongly inf
luences the catalytic behavior of gamma-Al2O3-supported vanadium oxide
catalysts during the ODH of n-butane and ethane. While the catalytic
activity in the ODH reactions increases with the vanadium loading, the
selectivity to the corresponding olefins shows a maximum for catalyst
s with 3-4 wt% V atoms. In addition, the selectivity to oxydehydrogena
tion products during the ODH of butane was lower than the selectivity
to ethene during the ODH of ethane. Associated VO4 tetrahedra were obs
erved by V-51-NMR on catalysts with V loading lower than 5 wt%, while
VO6 octahedra were predominant on catalysts with higher V loading. In
this way, although catalysts with octahedral V5+ species show higher c
atalytic activity, higher selectivity to oxydehydrogenation reactions
was achieved on catalysts in which mainly tetrahedral V5+ species were
observed. The number and nature of the acid sites also change with th
e vanadium loading. Thus, Lewis acid sites were observed mainly on cat
alysts with low V loading, while both Lewis and Bronsted acid sites we
re observed on catalysts with high V loading. Although V5+ species wer
e observed mainly on calcined samples, V4+ species are observed on tes
ted catalysts and their concentration depends on the alkane conversion
s used in the catalytic tests. (C) 1997 Academic Press.