Structural changes occurring at the surface of alumina-supported nanoscaled Mo–V–Nb–(Te)–O catalytic system during the selective oxidation of propane to acrylic acid

The effect of total coverage on alumina is evaluated for Mo5V4Nb1/Al2O3 catalysts by operando Raman-GC spectroscopy during reaction, demonstrating structural changes during reaction that do not occur during catalyst calcination. XRD detects show no appreciable change but Operando Raman-GC studies are sensitive to changes occurring in the nanometer scale, which modulate the performance during propane oxidation, delivering the structure–activity relationship for deactivation. Raman spectra confirm the formation of nanocrystalline MoO3-type structures during reaction up to 375 °C, accompanied by coke deposits, able to block the active sites, being detrimental for the acrylic acid formation. Three new catalysts were preparing by the addition of tellurium as dopant, in this case, the presence of MoO3 is not detected under reaction conditions, since the formation of a distorted rutile structure under reaction conditions is observed, and in this case acrylic acid is obtained as the main reaction product with a yield of ca. 25% at 400 °C.

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► Operando Raman-GC study of support-stabilized nanoscaled mixed oxides.
► The nature of entanglement between Mo and V ions determines catalytic activity.
► Reaction temperature transforms from mixed Mo–V–Al oxides (AlVMoO7).
► Mixed Mo–V–Al oxides are active for propane oxidation to acrylic acid.
► V-distorted alpha-MoO3 is not selective, producing COx.