On the nature of the active state of supported ruthenium catalysts used for the oxidation of carbon monoxide:: Steady-state and transient kinetics combined with in situ infrared spectroscopy

The oxidation of CO over Ru/MgO and Ru/SiO2 catalysts was used as a simple model reaction to derive turnover frequencies at atmospheric pressure, which were observed to agree with kinetic data obtained under high-vacuum conditions with supported ruthenium catalysts and the RuO2(110) single-crystal surface. Thus, it was possible to bridge both the pressure and the materials gap. However, a partial deactivation was observed initially, which was identified as an activated process, both under net reducing and net oxidizing conditions. Temperature-programmed reduction (TPR) experiments were performed subsequently in the same reactor, to monitor the degree of oxidation, as a function of the reaction temperature and the CO/O-2 reactant feed ratio. Using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements, the structural changes of the ruthenium catalysts during the oxidation of CO were confirmed, under relevant reaction conditions. Under net reducing conditions, only domains of RUO2 seem to exist on the metallic ruthenium particles, whereas, under net oxidizing conditions, the ruthenium particles were fully oxidized to bulk RuO2 particles, which may expose less-active facets, such as the RUO2(100) - c(2 x 2) surface.