Catalytic reactions of dioxygen with ethane and methane on platinum clusters: Mechanistic connections, site requirements, and consequences of chemisorbed oxygen

C2H6 reactions with O2 only form CO2 and H2O on dispersed Pt clusters at 0.2–28 O2/C2H6 reactant ratios and 723–913 K without detectable formation of partial oxidation products. Kinetic and isotopic data, measured under conditions of strict kinetic control, show that CH4 and C2H6 reactions involve similar elementary steps and kinetic regimes. These kinetic regimes exhibit different rate equations, kinetic isotope effects and structure sensitivity, and transitions among regimes are dictated by the prevalent coverages of chemisorbed oxygen (O*). At O2/C2H6 ratios that lead to O*-saturated surfaces, kinetically-relevant Csingle bondH bond activation steps involve O*single bondO* pairs and transition states with radical-like alkyls. As oxygen vacancies (∗) emerge with decreasing O2/alkane ratios, alkyl groups at transition states are effectively stabilized by vacancy sites and Csingle bondH bond activation occurs preferentially at O*single bond* site pairs. Measured kinetic isotope effects and the catalytic consequences of Pt cluster size are consistent with a monotonic transition in the kinetically-relevant step from Csingle bondH bond activation on O*single bondO* site pairs, to Csingle bondH bond activation on O*single bond* site pairs, to O2 dissociation on *single bond* site pairs as O* coverage decrease for both C2H6 and CH4 reactants. When Csingle bondH bond activation limits rates, turnover rates increase with increasing Pt cluster size for both alkanes because coordinatively unsaturated corner and edge atoms prevalent in small clusters lead to more strongly-bound and less-reactive O* species and lower densities of vacancy sites at nearly saturated cluster surfaces. In contrast, the highly exothermic and barrierless nature of O2 activation steps on uncovered clusters leads to similar turnover rates on Pt clusters with 1.8–8.5 nm diameter when this step becomes kinetically-relevant at low O2/alkane ratios. Turnover rates and the O2/alkane ratios required for transitions among kinetic regimes differ significantly between CH4 and C2H6 reactants, because of the different Csingle bondH bond energies, strength of alkylsingle bondO* interactions, and O2 consumption stoichiometries for these two molecules. Vacancies emerge at higher O2/alkane ratios for C2H6 than for CH4 reactants, because their weaker Csingle bondH bonds lead to faster scavenging of O* and to lower O* coverages, which are set by the kinetic coupling between Cdouble bond; length as m-dashH and Odouble bond; length as m-dashO activation steps. The elementary steps, kinetic regimes, and mechanistic analogies reported here for C2H6 and CH4 reactions with O2 are consistent with all rate and isotopic data, with their differences in Csingle bondH bond energies and in alkyl binding, and with the catalytic consequences of surface coordination and cluster size. The rigorous mechanistic interpretation of these seemingly complex kinetic data and cluster size effects provides useful kinetic guidance for larger alkanes and other catalytic surfaces based on the thermodynamic properties of these molecules and on the effects of metal identity and surface coordination on oxygen binding and reactivity.