Oxygen adsorption and oxidation reactions on Au(211) surfaces:: Exposures using O2 at high pressures and ozone (O3) in UHV

Nanosized gold particles supported on reducible metal oxides have been reported to show high catalytic activity toward CO oxidation at low temperature. This has generated great scientific and technological interest, and there have been many proposals to explain this unusual activity. One intriguing explanation that can be tested is that of Norskov and coworkers [Catal. Lett. 64 (2000) 101] who suggested that the "unusually large catalytic activity of highly-dispersed An particles may in part be due to high step densities on the small particles and/or strain effects due to the mismatch at the Au-support interface". In particular, their calculations indicated that the Au(211) stepped surface would be much more reactive towards O-2 dissociative adsorption and CO adsorption than the Au(111) surface. We have now studied the adsorption of O-2 and O-3 (Ozone) on an Au(211) stepped surface. We find that molecular oxygen (02) was not activated to dissociate and produce oxygen adatoms on the stepped Au(211) surface even under high-pressure (700 Torr) conditions with the sample at 300-450 K. Step sites do bind oxygen adatoms more tightly than do terrace sites, and this was probed by using temperature programmed desorption (TPD) of O-2 following ozone (O-3) exposures to produce oxygen adatoms up to a saturation coverage of theta(O) = 0.90 ML. In the low-coverage regime (theta(O) <= 0.15 ML), the O-2 TPD peak at 540 K, which does not shift with coverage, is attributed to oxygen adatoms that are bound at the steps on the Au(2 11) surface. At higher coverages, an additional lower temperature desorption peak that shifts from 515 to 530 K at saturation coverage is attributed to oxygen adsorbed on the (111) terrace sites of the Au(2 11) surface. Although the desorption kinetics are likely to be quite complex, a simple Redhead analysis gives an estimate of the desorption activation energy, E-d, for the step-adsorbed oxygen of 34 kcal/mol and that for oxygen at the terraces near saturation coverage of 33 kcal/mol, values that are similar to others reported on An surfaces. Low Energy Electron Diffraction (LEED) indicates an oxygen-induced step doubling on the Au(211) surface at low-coverages (theta(O) = 0.08-0.17 ML) and extensive disruption of the 2D ordering at the surface for saturation coverages of oxygen (theta(O) > 0.9 ML). Overall, our results indicate that unstrained step sites on Au(211) surfaces of dispersed An nanoparticles do not account for the novel reactivity of supported Au catalysts for CO oxidation. (c) 2006 Elsevier B.V. All rights reserved.