Natalia Martin

In Situ X-Ray Photoelectron Spectroscopy of Model Catalysts : At the Edge of the Gap

We present high-pressure x-ray photoelectron spectroscopy (HP-XPS) and first-principles kinetic Monte Carlo study addressing the nature of the active surface in CO oxidation over Pd(100). Simultaneously measuring the chemical composition at the surface and in the near-surface gas phase, we reveal both O-covered pristine Pd(100) and a surface oxide as stable, highly active phases in the near-ambient regime accessible to HP-XPS. Surprisingly, no adsorbed CO can be detected during high CO(2) production rates, which can be explained by a combination of a remarkably short residence time of the CO molecule on the surface and mass-transfer limitations in the present setup.

Effects of non-local exchange on core level shifts for gas-phase and adsorbed molecules

Density functional theory calculations are often used to interpret experimental shifts in core level binding energies. Calculations based on gradient-corrected (GC) exchange-correlation functionals are known to reproduce measured core level shifts (CLS) of isolated molecules and metal surfaces with reasonable accuracy. In the present study, we discuss a series of examples where the shifts calculated within a GC-functional significantly deviate from the experimental values, namely the CLS of C 1s in ethyl trifluoroacetate, Pd 3d in PdO and the O 1s shift for CO adsorbed on PdO(101). The deviations are traced to effects of the electronic self-interaction error with GC-functionals and substantially better agreements between calculated and measured CLS are obtained when a fraction of exact exchange is used in the exchange-correlation functional.

A high pressure x-ray photoelectron spectroscopy study of CO oxidation over Rh(100).

We have studied the oxidation of CO over Rh(100) using high pressure x-ray photoelectron spectroscopy under CO and O2 pressures ranging from 0.01 to 1xa0mbar. The results show a very low or no conversion for the CO covered surface found at low temperatures, while the activity rises slightly when the temperature is high enough for some CO to desorb, exposing surface sites for dissociative O2 adsorption. As the temperature is increased further, more CO desorbs and oxygen replaces CO as the dominating species at the surface. At the same time we find a sudden increase in the reactivity, such that all CO that reaches the surface is instantly transformed into CO2. We find that the O coverage in the active state is highly dependent on the total pressure and, although we do not detect any presence of a surface oxide as in previous surface x-ray diffraction studies, the highest O coverage indicates that the surface is close to being oxidized.