CO oxidation studied using 'fast' XPS and a molecular beam reactor

We have combined the use of a molecular beam reactor with 'fast' XPS in order to correlate changes in the rate of CO oxidation with the coverages of the adsorbates and intermediates on the surface. In the reactor CO oxidation exhibits an isothermal 'light-off' phenomenon in which the rate autocatalytically increases with time. This is due to the desorption of CO which releases extra sites for O-2 dissociation which, in turn, removes more CO, and hence the self-acceleration. In effect the reaction can be written as 2CO(a) + O-2g + 2S -> 2CO(2g) + 4S, the acceleration coming from the release of extra adsorption sites, S, which are involved in the reaction itself. 'Fast XPS', carried out in-situ during the course of the reaction, shows domination of the surface by COa below 390 K and by Oa above that temperature, with a rapid change in surface coverage over a very narrow temperature window. This is an advance on earlier work, since our measurements are made in a single, continuous experiment, due to the high brightness of the synchrotron source. This also allows the data to be obtained at high energy resolution, in the presence of both gases, and without contamination. On high surface area samples this acceleration is further reinforced due to a rapid temperature increase because of the highly exothermic nature of the overall reaction.