The Role of Oxides in Catalytic CO Oxidation over Rhodium and Palladium

Catalytic CO oxidation is a seemingly simple reaction between CO and O2 molecules, one of the reactions in automotive catalytic converters, and the fruit-fly reaction in model catalysis. Surprisingly, the phase responsible for the catalytic activity is still under debate, despite decades of investigations. We have performed a simple but yet conclusive study of single crystal Rh and Pd model catalysts, resolving this controversy. For Rh, the oxygen-covered metallic surface is more active than the oxide, while for Pd, thin oxidefilms are at least as active as the metallic surface, but a thicker oxide is less active. Apart from resolving a long-standing debate, our results pinpoint important design principles for oxidation catalysts as to prevent catalytic extinction at high oxygen exposures.