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The Langmuir-Hinshelwood barrier (ELH) and the pre-exponential factor($\nu$LH) for CO oxidation have been measured at high temperature on hexagonalarrays of Pd clusters supported on an ultrathin alumina film on Ni3Al(111). ThePd clusters have a sharp size distribution and the mean sizes are: 174$\pm$13,360$\pm$19 and 768$\pm$28 atoms. ELH and $\nu$LH are determined from theinitial reaction rate of a CO molecular beam with a saturation layer ofadsorbed oxygen on the Pd clusters, measured at different temperatures(493$\le$T (K) $\le$613). The largest particles (3.5 nm) give values of ELH and$\nu$LH similar to those measured on Pd (111) [2]. However, smaller particles(2.7 and 2.1 nm) show very different behavior. The origin of this size effectis discussed in terms of variation of the electronic structure and of theatomic structure of the Pd clusters.

Particle size effect on the Langmuir-Hinshelwood barrier for CO oxidation on regular arrays of Pd clusters supported on ultrathin alumina films