Bulk oxidation state of the different cationic elements in the MoVTe(Sb)NbO catalysts for oxidation or ammoxidation of propane

Different spectroscopic techniques like XANES, ESR, XPS and Mossbauer spectroscopy have been used to determine the oxidation state of the various cations in the M1 and M2 phases of the MoVTe(Sb)NbO catalysts used for the oxidation or ammoxidation of propane. It was observed that the tellurium or antimony M 1o rM2 phases contained mainly Te IV , and Nb V. Molybdenum, vanadium and antimony were shown to be present as Mo VI and Mo V ,V V and V IV and Sb V and Sb III . The M1 phase which is responsible for the high efficiency of catalysts, corresponds to the total stoichiometry (AO)2� x(A2O)xM20O56 with A = Sb or Te, M = Mo, V and Nb and 0 � x � 1. It has a structure with hexagonal channels occupied by the A cations and oxides. This channel may contain an excess of oxygen which constitutes a reservoir for the catalysts and which likely plays a role in the reoxidation of the catalytic sites. The balance of the charges introduced by these oxides anions was achieved by the partial oxidation of Sb III to Sb V in M1(Sb) and by the oxidation of Mo V to Mo VI in M1(Te), Te remaining always Te IV as shown from Mossbauer spectroscopy data. The characterization of the solids after catalytic test showed very few changes in the solids structures and compositions. The study allowed concluding that the lone pair elements does not have only a role as constituents of the surface catalytic sites but also as bulk components to store oxygen in the hexagonal channels and contributes to its rapid diffusion to the surface. # 2004 Elsevier B.V. All rights reserved. reported as (Te2O)2M20O56 and (SbO)2M20O56 with M = Mo, V, Nb. The V/Mo and Nb/Mo ratios can vary, but are most frequently close to 0.3 and 0.1, respectively (4,5). The phase containing Te has an oxide over- stoichiometry while the one containing Sb, an oxide sub- stoichiometry, they may better be reported with the general composition (AO)2� x(A2O)xM20O56 with A = Te or Sb and 0 � x � 1. The first structure model for the M1 phases has been proposed in 2002 based on an isomorphism with the phase Cs0.7(Nb,W)5O14 (4). The structure of the M1 phase has been described as a corner sharing MO6 (M = Mo, V, Nb) octahedra network with tellurium or antimony cations and oxygen anions occupying sites in hexagonal channels formed by the octahedra. Besides hexagonal channels, pentagonal and heptagonal channels are present and oriented in the same direction. The heptagonal channels have been