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Combining molecular beam techniques and time-resolved infrared reflection absorption spectroscopy ͑TR-IRAS͒ we have studied the kinetics of the CO oxidation reaction on an alumina-supported Pd model catalyst. The Pd particles are deposited by metal evaporation under ultrahigh vacuum ͑UHV͒ conditions onto a well-ordered alumina film, prepared on a NiAl͑110͒ single crystal. Particle size, density and structure of the Pd deposits have been characterized in previous studies. In the low temperature region, transient and steady-state experiments have been performed over a wide range of CO and oxygen fluxes by crossing two effusive molecular beams on the sample surface. We determine the steady-state CO 2 production rate as a function of the CO fraction in the impinging gas flux. Simultaneously, the occupation of CO adsorption sites under steady-state conditions is monitored by in situ IR spectroscopy. The origin of different types of CO 2 transients is discussed. In particular we focus on the transient CO 2 production after switching off the CO beam. For the model catalyst investigated, detailed reaction rate measurements in combination with time-resolved IRAS show that the origin of the particular transient behavior of the supported model system is not due to the presence of specific adsorption sites on small particles, as has been proposed previously. Instead, we show that the transient behavior can be semiquantitatively simulated on the basis of a simple kinetic model considering a homogeneous surface, and accounting for the inhibition of the dissociative adsorption of O 2 at high CO coverage. Moreover, it is discussed how the inherent heterogeneity of the supported particle system can additionally enhance the observed effect.

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