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The reaction of NO and CO on Pt(100) exhibits two branches of steady state production of N2 and CO2 and the occurrence of kinetic oscillations. This system was studied under steady flow conditions in the 10−6 mbar total pressure range using low-energy electron diffraction-(LEED), work function measurement, and mass spectrometry for determination of the reaction rate. These studies revealed that kinetic oscillations can only be initiated from one of the two stable reaction branches. Two separate existence regions were detected in which the oscillations are always damped. Oscillations can be very reproducibly excited by slight decreases in temperature. The 1×1■hex phase transition of the surface structure was observed to take place only in one of the two regions of reaction rate oscillations. Its influence seems to be of minor relevance to the mechanism of oscillations as oscillations in one region occur on the surface that maintains a 1×1 structure. The experiments were modeled by a set of coupled differential equations based on knowledge about the elementary reaction steps. The model calculations reproduced the steady states of the reaction as well as the occurrence of kinetic oscillations in different ranges in excellent agreement with experimental observation. In the model, the phase transition also has no relevance for the oscillation mechanism. The occurrence of oscillations can be rationalized in terms of a periodic sequence of autocatalytic ‘‘surface explosions’’ and the restoration of an adsorbate-covered surface. The damping, experimentally observed, is attributed to insufficient spatial coupling between different regions of the surface.

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Experimental investigations on the catalytic oxidation of CO on well-defined Pt(100) surfaces at low pressures (∼10−4 Torr) revealed under certain conditions the occurrence of kinetic oscillations which were associated with periodic transformations of the surface structure propagating wave-like across the surface area. Based on experimental information about the various elementary steps involved (adsorption, desorption, surface reaction, adsorbate-induced surface structural transformation) a set of coupled differential equations describing the kinetics of the various processes was established. A simplified version of these equations allows analytical treatment and provides qualitative insight into the occurrence of oscillations through linear stability analysis. Numerical solution of the full set of reaction-diffusion equations reproduces the essential spatio-temporal features of the experimental observations, although full quantitative agreement would still require better adjustment of the parameters involved as well as further refinement of the model.

In catalytic methanol oxidation on ultrathin vanadium oxide layers on Rh(111) (Θ_{V}≈0.2 monolayer equivalent) we observe a 2D ripening of the VO_{x} islands that is controlled by the catalytic reaction. Neighboring VO_{x} islands move under reaction conditions towards each other and coalesce. The motion and the coalescence of the islands are explained by a polymerization-depolymerization equilibrium that is sensitive to gradients in the adsorbate coverages.

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Catalytic ammonia oxidation over platinum has been studied experimentally from UHV up to atmospheric pressure with polycrystalline Pt and with the Pt single crystal orientations (533), (443), (865), and (100). Density functional theory (DFT) calculations explored the reaction pathways on Pt(111) and Pt(211). It was shown, both in theory and experimentally, that ammonia is activated by adsorbed oxygen, i.e. by O(ad) or by OH(ad). In situ XPS up to 1 mbar showed the existence of NH(x)(x= 0,1,2,3) intermediates on Pt(533). Based on a mechanism of ammonia activation via the interaction with O(ad)/OH(ad) a detailed and a simplified mathematical model were formulated which reproduced the experimental data semiquantitatively. From transient experiments in vacuum performed in a transient analysis of products (TAP) reactor it was concluded that N(2)O is formed by recombination of two NO(ad) species and by a reaction between NO(ad) and NH(x,ad)(x= 0,1,2) fragments. Reaction-induced morphological changes were studied with polycrystalline Pt in the mbar range and with stepped Pt single crystals as model systems in the range 10(-5)-10(-1) mbar.