A density functional theory study of the oxidation of methanol to formaldehyde over vanadia supported on silica, titania and zirconia

The mechanism of the selective oxidation of methanol to formaldehyde over vanadia supported on silica, titania and zirconia, suggested recently by Khaliullin and Bell, has been critically reconsidered at the same density functional theory (B3LYP/6-31G*) level. It was shown that an improper use of cluster models mimicking an intrinsic support structure may result in the failure to explain the observed experimental findings like those found in the above paper, i.e. when considering the activation energies and TOF between those three different supports, as well as the next-nearestneighbor V environment geometry for vanadia supported on titania catalyst.