Reaction pathway of benzonitrile formation during toluene ammoxidation on vanadium phosphate catalysts

The reaction pathway of the ammoxidation of toluene on (VO)₂P₂O₇ used as catalyst and the interaction of potential intermediates with the pyrophosphate were studied by spectroscopic techniques (FTIR, EPR), temperature-programmed chemisorptions/ reactions (TPD, TPRS) and transient studies such as the temporal analysis of products (TAP) technique. NH₃ is chemisorbed on the catalyst surface, forming three different species, i.e., NH₄⁺ ions located on BrØnsted sites, coordinatively bound NH₃ on Lewis sites and NH₂^– groups, presumably P-NH₂. Toluene that is probably adsorbed on Lewis sites reacts in a first step to a benzyl radical. A subsequent partial oxidation by interaction of V^IV=O groups generates a V...O=CH-C₆H₅ surface structure. This benzaldehyde-like surface species reacts with adsorbed NH₃ according to a Langmuir-Hinshelwood mechanism. TAP experiments on ammonium-containing vanadium phosphates revealed that NH₄⁺ ions could act as potential N-insertion species. No formation of benzylamine as well as the generation of V=NH surface groups as possible intermediates or N-insertion sites were observed.