The adsorption of NO on an oxygen pre-covered Pt(1 1 1) surface: in situ high-resolution XPS combined with molecular beam studies

Adsorption of NO on a Pt(1 1 1) surface pre-covered with a p(2 × 2) atomic oxygen layer has been studied in situ by high-resolution X-ray photoelectron spectroscopy and temperature-programmed XPS using third-generation synchrotron radiation at BESSY II, Berlin, combined with molecular beam techniques and ex situ by low energy electron diffraction and temperature-programmed desorption. O 1s XP spectra reveal that an ordered p(2 × 2)-O layer dramatically changes the adsorption behavior of NO as compared to the clean surface. The atomic oxygen occupies fcc hollow sites, and therefore blocks NO adsorption on these sites, which are energetically preferred on clean Pt(1 1 1). As a consequence, NO populates on-top sites at low coverage. At 110 K for higher coverages, NO can additionally adsorb on hcp hollow sites, thereby inducing a shift of the O 1s binding energy of atomic oxygen towards lower energies by about 0.25 eV. The bond strength of the hcp hollow NO species to the substrate is weakened by the presence of atomic oxygen. A sharp p(2 × 2) LEED pattern is observed for NO adsorption on the oxygen pre-covered surface, up to saturation coverage. The total saturation coverage of NO on Pt(1 1 1) pre-covered with varying amounts of oxygen (below 0.25 ML) decreases linearly with the coverage of oxygen. The initial sticking coefficient of NO is reduced from 0.96 on clean Pt(1 1 1) to 0.88 on a p(2 × 2) oxygen pre-covered surface.