Influence of electronic properties of Na2O/CaO catalysts on their catalytic characteristics for the oxidative coupling of methane

For Na₂O/CaO catalysts of different sodium content the adsorption of oxygen and their electrical properties were studied by transient experiments and measurements of contact potential differences (CPD) as well as electrical conductivity. CPD results show a change of the mechanism of oxygen activation with increasing sodium concentration due to changing the type of ionic conductivity from cationic to anionic. Anion vacancies are formed by incorporation of sodium into the CaO lattice. As CPDs show, the cation conductivity promotes an accumulation of oxygen species on the catalyst surface resulting in a decrease of C₂ product selectivity for the catalyzed oxidative coupling of methane. The anion conductivity favors a dissociation of molecular adsorbed oxygen and a subsequent incorporation into the oxide lattice, hereby, decreasing its concentration on the catalyst surface which favors in term selective formation of ethane and ethylene. This revised version was published online in July 2006 with corrections to the Cover Date.