Adsorption and reaction of acetylene on clean and oxygen-precovered Pd(100) studied with high-resolution X-ray photoelectron spectroscopy.

We investigated the adsorption and thermal evolution of acetylene on clean Pd(100) and Pd(100) precovered with 0.25 ML oxygen. The measurements were performed in situ by fast XPS at the synchrotron radiation facility BESSY II. On Pd(100) acetylene molecularly adsorbs at 130 K. Upon heating transformation to a CCH species occurs around 390 K along with the formation of a completely dehydrogenated carbon species. On the oxygen-precovered surface partial CCH formation already occurs upon adsorption at 130 K, and the dehydrogenation temperature and the stability range of CCH are shifted to lower temperatures by ∼200 K.

Ultrafast x-ray photoelectron spectroscopy in the microsecond time domain.

We introduce a new approach for ultrafast in situ high-resolution X-ray photoelectron spectroscopy (XPS) to study surface processes and reaction kinetics on the microsecond timescale. The main idea is to follow the intensity at a fixed binding energy using a commercial 7 channeltron electron analyzer with a modified signal processing setup. This concept allows for flexible switching between measuring conventional XP spectra and ultrafast XPS. The experimental modifications are described in detail. As an example, we present measurements for the adsorption and desorption of CO on Pt(111), performed at the synchrotron radiation facility BESSY II, with a time resolution of 500 µs. Due to the ultrafast measurements, we are able to follow adsorption and desorption in situ at pressures of 2 × 10(-6) mbar and temperatures up to 500 K. The data are consistently analyzed using a simple model in line with data obtained with conventional fast XPS at temperatures below 460 K. Technically, our new approach allows measurement on even shorter timescales, down to 20 µs.

Gold intercalation of boron-doped graphene on Ni(111): XPS and DFT study.

The intercalation of a graphene layer adsorbed on a metal surface by gold or other metals is a standard procedure. While it was previously shown that pristine, i.e., undoped, and nitrogen-doped graphene sheets can be decoupled from a nickel substrate by intercalation with gold atoms in order to produce quasi-free-standing graphene, we find the gold intercalation behavior for boron-doped graphene on a Ni(111) surface to be more complex: for low boron contents (2-5%) in the graphene lattice only partial gold intercalation occurs and for higher boron contents (up to 20%) no intercalation is observed. In order to understand this different behavior, a density functional theory investigation is carried out, comparing undoped as well as substitutional nitrogen- and boron-doped graphene on Ni(111). We identify the stronger binding of the boron atoms to the nickel substrate as the factor responsible for the different intercalation behavior in the case of boron doping. However, the calculations predict that this energetic effect prevents the intercalation process only for large boron concentrations and that it can be overcome for smaller boron coverages, in line with our x-ray photoelectron spectroscopy experiments.