In Situ Optical Reflectance Difference Observations of CO Oxidation over Pd(100).

Using a home-built reflectometer, we have investigated the changes in the optical reflectivity of a Pd(100) model catalyst during CO oxidation under high-pressure, high-temperature conditions. We observe changes in optical contrast when exposing the surface to CO oxidation conditions at 200 mbar from room temperature up to 400 °C. These changes in reflectivity are a result both of the formation of a surface oxide layer and of a change in surface roughness because of gas exposure. However, the reflectivity is more sensitive to the presence of a thin, flat oxide layer than to surface roughness. CO oxidation plays an important role in the decrease of the reflectivity. Since adding a reducing agent to the gas mixture renders it unlikely that the oxide thickness increases, we conclude that the observed decrease in reflectivity is dominated by increased surface roughness because of the catalytic reaction. We contribute this observed surface roughening to a Mars-van Krevelen-type reaction mechanism.