Catalytic combustion of methane over alumina-supported palladium: Relationships between the oxidation state, particle size, morphology and activity

Supported palladium was studied as a catalyst for combustion of natural gas. The influence of variations in temperature and oxygen concentration, of addition of CO and water and of in situ hydrogen reduction on catalyst activity was studied experimentally. The activation energy for methane oxidation over crystalline PdO is about 17.5 kcal/mole and over metallic Pd - 40--45 kcal/mole. The difference in the activation energy is compensated by the preexponential coefficient that is 5--6 orders of magnitude higher for Pd than for PdO. In this work the activity variations under the different reaction conditions were correlated with the corresponding changes in the catalyst oxidation state, particle size and morphology.; Formation of metallic hexagonal crystallites 100--200 nm in size was observed by TEM after PdO reduction, which resulted in an increase in the catalyst activity. Redispersion of these metallic crystallites into PdO clusters of 3--5 nm in size occurred during the Pd reoxidation, which resulted in a reversible increase of the catalyst activity on the cooling cycle, known as "negative activation."; Activation of the methane molecule is the limiting step of the reaction over both the Pd and the PdO states. We propose that on the Pd surface the reaction occurs through the Langmuir-Hinshelwood mechanism. Under conditions of catalytic combustion the surface is completely covered with oxygen and competitive dissociative adsorption of methane is the limiting step of the process. The high heat of oxygen adsorption explains the high activation energy for the overall process. On the PdO surface the reaction occurs through a redox mechanism. A methane molecule interacts with a surface Pd-O dimer resulting in adsorbed CH3 and OH species. The activation energy of this interaction is about 15 kcal/mole and the probability is low due to the different multiplicity of the initial and final states of the transition complex.; Oscillations in the reaction rate under fuel-rich mixtures at temperatures where the metallic phase of the catalyst was stable were observed and their mechanism is discussed. For the cc-alumina supported Pd an instant, though fully recoverable, decrease in the catalyst activity was observed after water vapor was added to the mixture. No effect of CO on the catalyst activity was found. Severe corrosion of the surface of Pd foil occurred under reaction conditions.