A detailed spectroscopic analysis of the growth of oxy-carbon species on the surface of Pt/Al2O3 during propane oxidation

The growth of oxygenated carbonaceous (oxy-carbon) species on the surface of Pt/Al2O3 during total oxidation of propane is analyzed in detail—including their composition, their location on the catalyst surface, their reactivity, and their role in the propane oxidation mechanism—by in situ diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS). Platinum nanoparticles catalyze the transformation of propane into many different oxy-carbon surface species, including acetate, enolate, aliphatic ester, and acetone, which spillover and grow on the Al2O3 support. There is no correlation between the concentration of oxy-carbon surface species and the rate of CO2 production in the gas-phase, which indicates that these species are inert spectators in the propane oxidation mechanism. Temperature-programmed oxidation of the oxy-carbon surface species reveals that enolate, aliphatic ester, and acetone species are removed from the surface by combustion at similar temperatures with an activation barrier of 112 kJ/mol, whereas acetate species are removed at higher temperatures with an activation barrier of 147 kJ/mol. Both the formation and combustion of oxy-carbon surface species occur in pathways that are parallel to, and orders-of-magnitude slower than, the main pathway to CO2 production.