RESUMEN
X-ray photoemission spectroscopy is a standard technique for materials characterization and the O 1s binding energy is commonly measured for oxides. Here we use density functional theory calculations to investigate how the O 1s binding energy in CeO2(111) is influenced by the presence of oxygen vacancies. The case with point vacancies in CeO2(111) is compared to complete reduction to Ce2O3. Reduction of CeO2by oxygen vacancies is found to have a minor effect on the O 1s binding energy. The O 1s binding energy is instead clearly changed when the character of the chemical bond for the considered oxygen atom is modified by, for example, the formation of OH-groups or carbonates.
RESUMEN
Pt/ZrO2 model catalysts were prepared by atomic layer deposition (ALD) and examined at mbar pressure by operando sum frequency generation (SFG) spectroscopy and near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) combined with differentially pumped mass spectrometry (MS). ALD enables creating model systems ranging from Pt nanoparticles to bulk-like thin films. Polarization-dependent SFG of CO adsorption reveals both the adsorption configuration and the Pt particle morphology. By combining experimental data with ab initio density functional theory (DFT) calculations, we show that the CO reaction onset is determined by a delicate balance between CO disproportionation (Boudouard reaction) and oxidation. CO disproportionation occurs on low-coordinated Pt sites, but only at high CO coverages and when the remaining C atom is stabilized by a favorable coordination. Thus, under the current conditions, initial CO oxidation is found to be strongly influenced by the removal of carbon deposits formed through disproportionation mechanisms rather than being determined by the CO and oxygen inherent activity. Accordingly, at variance with the general expectation, rough Pt nanoparticles are seemingly less active than smoother Pt films. The applied approach enables bridging both the "materials and pressure gaps".
