Catalytic dehydrogenation of propane to propene over platinum and platinum-gold alloys

Abstract

The rates of dehydrogenation of propane to propene over platinum and very dilute platinumin-gold alloys have been measured. In the composition range of 0.5–14.0 atom % platinum, the rates per unit surface area of the alloy powders vary linearly with the bulk platinum concentration in the alloys. From this it is concluded that only one platinum atom is involved in the rate-determining step. For both platinum and the alloys, activation energies of some 29 ± 2 kcal/mole were measured. The reaction rate order in hydrogen, however, is different. It is proposed that propane dehydrogenation over platinum and over the alloys occurs via the same reaction mechanism, namely, dissociative chemisorption of propane on a single platinum atom to which two adsorption sites are associated, one of which carries a hydrogen atom. The subsequent conversion of the propyl radical into π-bonded propene via β-hydrogen elimination appears to be rate determining. The last step, desorption of π-bonded propene, has a comparatively low activation energy. The difference in negative reaction order, with respect to hydrogen, between platinum and its diluted alloys reflects a lower steady-state θ H on Pt atoms surrounded by Au atoms vis-à-vis Pt atoms on a Pt surface.