We demonstrate that the (local) adsorbed carbon monoxide, COad, coverage on the Pt-free areas of bimetallic Pt/Ru(0001) surfaces (a Ru(0001) substrate partly covered by Pt monolayer islands) can be increased to ∼0.80 monolayers (ML), well above the established saturation COad coverage of 0.68 ML, even under ultrahigh vacuum conditions by using spill-over of CO adsorbed on the Pt islands to the Ru areas as an highly effective adsorption channel. The apparent COad saturation coverage of 0.68 ML on pure Ru(0001) is identified as due to kinetic limitations, hindering further uptake from the gas phase, rather than being caused by thermodynamic reasons. This spill-over mechanism is proposed to be a general phenomenon for adsorption on bimetallic surfaces.
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