Abstract
The interaction of PuO2, UO2+x and UO3 with water ice was studied using ultraviolet photoelectron spectroscopy (UPS). Water was adsorbed at 80–120 K as thick ice multilayers. Surface modification after desorption of the ice around 200 K was investigated. Main information on the surface oxidation state was obtained by highly surface sensitive UPS-HeII spectra, probing primarily the first monolayer. The oxidation state was directly deduced from the intensity of the actinide 5f levels. The surface character of the phenomenon was further confirmed by comparing HeII spectra with the more bulk sensitive HeI spectra. Spectral interpretation was done using the cross-section variations in HeI and HeII spectra and by comparing the spectra with theoretical density of states curves, obtained by LSDA + U calculations. It was shown previously that reduction to Pu2O3 takes place, when the ice covered PuO2 films are warmed up under UV light and ice is desorbed. In this paper, this effect was investigated in further detail. It was shown that only the top surface layer is reduced. Reduction is inhibited by surface diffusion of oxygen trapped in the films during sputter deposition and not incorporated in the lattice. UO2+x and UO3 also undergo reduction, but to a significant lesser extent than PuO2. Reoxidation of surface U by bulk oxygen was much slower than that of surface Pu. It was shown that for all oxides, reduction needs the illumination of an ice overlayer by UV light. Surface reduction by atomic hydrogen was investigated to check for possible influence of ice photolysis products. UO3 was shown to be reduced to UO2 while PuO2 is not further reduced. The observations are explained by photochemical decomposition of water by the UV light (used for UPS) at the oxide-ice interface. It is thought that the oxide acts as photocatalyst, absorbing light and splitting adsorbed water. The thick ice layer traps the reaction products on the surface, thereby enabling them to react and reduce the surface. Why only the reductants (probably H) and not the concomitant oxidants react with the surface is still unknown.
Published Version
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