Vanadium oxides on aluminum oxide supports. 2. Structure, vibrational properties, and reducibility of V2O5 clusters on alpha-Al2O3(0001)

The structure, stability, and vibrational properties of isolated V2O5 clusters on the Al2O3(0001) surface have been studied by density functional theory and statistical thermodynamics. The most stable structure does not possess vanadyl oxygen atoms. The positions of the oxygen atoms are in registry with those of the alumina support, and both vanadium atoms occupy octahedral sites. Another structure with one vanadyl oxygen atom is only 0.12 eV less stable. Infrared spectra are calculated for the two structures. The highest frequency at 922 cm(-1) belongs to a V-O stretch in the V-O-Al interface bonds, which supports the assignment of such a mode to the band observed around 941 cm(-1) for vanadia particles on alumina. Removal of a bridging oxygen atom from the most stable cluster at the V-O-Al interface bond costs 2.79 eV. Removal of a (vanadyl) oxygen atom from a thin vanadia film on alpha-Al2O3 costs 1.3 eV more, but removal from a V2O5(001) single-crystal surface costs 0.9 eV less. Similar to the V2O5(001) surface, the facile reduction is due to substantial structure relaxations that involve formation of an additional V-O-V bond and yield a pair of V(IV)(d1) sites instead of a V(III)(d2)/V(V)(d0) pair.