Ordering of point defects in VPO precursors: Effect on doping and catalyst performance

The kind and percentage of point defects in commercial as well as laboratory prepared hemihydrate VPO precursors have been analysed using a combination of electron diffraction experiments and diffraction pattern simulation. Experimental patterns reveal the systematic existence of kinematically forbidden reflections that are attributed to vacant lattice sites in the VOHPO4·1/2H2O matrix. The vacancies are associated with vanadium ions and are distributed into the bulk and surface of hemihydrate in an ordered fashion. The amount of vacancies is in similar proportion between the two precursors studied. A considerable enhancement in the forbidden reflections intensity in doped hemihydrate samples has been experimentally observed, which is attributed to the partial substitution of dopant ions into V vacant sites. The beneficial effect of such a modified hemihydrate structure on the resulting VPO catalyst performance is demonstrated, since the facilitation of promoter incorporation in V-based vacant active sites brings upon an enhanced activity and selectivity for the catalyst.

Graphical abstractThe systematic existence of kinematically forbidden reflections in experimental diffraction patterns of hemihydrate VPO precursors is attributed to ordered vanadium vacancies. Such modified precursor structures are shown to effectively facilitate promoter incorporation into the bulk and surface of the crystal and significantly enhance the activity and selectivity of VPO catalysts.Figure optionsDownload full-size imageDownload high-quality image (30 K)Download as PowerPoint slide