Selective oxidation of propylene to acrolein over supported V2O5/Nb2O5 catalysts: An in situ Raman, IR, TPSR and kinetic study

The vapor-phase selective oxidation of propylene (H2Cdouble bond; length as m-dashCHCH3) to acrolein (H2Cdouble bond; length as m-dashCHCHO) was investigated over supported V2O5/Nb2O5 catalysts. The catalysts were synthesized by incipient wetness impregnation of V-isopropoxide/isopropanol solutions and calcination at 450 °C. The catalytic active vanadia component was shown by in situ Raman spectroscopy to be 100% dispersed as surface VOx species on the Nb2O5 support in the sub-monolayer region (<8.4 V/nm2). Surface allyl species (H2Cdouble bond; length as m-dashCHCH2*) were observed with in situ FT-IR to be the most abundant reaction intermediates. The acrolein formation kinetics and selectivity were strongly dependent on the surface VOx coverage. Two surface VOx sites were found to participate in the selective oxidation of propylene to acrolein. The reaction kinetics followed a Langmuir–Hinshelwood mechanism with first-order in propylene and half-order in O2 partial pressures. C3H6-TPSR spectroscopy studies also revealed that the lattice oxygen from the catalyst was not capable of selectively oxidizing propylene to acrolein and that the presence of gas phase molecular O2 was critical for maintaining the surface VOx species in the fully oxidized state. The catalytic active site for this selective oxidation reaction involves the bridging Vsingle bondOsingle bondNb support bond.