Spectroscopic link between adsorption site occupation and local surface chemical reactivity.
In this Letter we show that sequences of adsorbate-induced shifts of surface core level (SCL) x-ray photoelectron spectra contain profound information on surface changes of electronic structure and reactivity. Energy shifts and intensity changes of time-lapsed spectral components follow simple rules, from which adsorption sites are directly determined. Theoretical calculations rationalize the results for transition metal surfaces in terms of the energy shift of the d-band center of mass and this proves that adsorbate-induced SCL shifts provide a spectroscopic measure of local surface reactivity.
O- and H-induced surface core level shifts on Ru(0001): prevalence of the additivity rule
In previous work on adsorbate-induced surface core level shifts (SCLSs), the effects caused by O atom adsorption on Rh(111) and Ru(0001) were found to be additive: the measured shifts for first-layer Ru atoms depended linearly on the number of directly coordinated O atoms. Density-functional theory calculations quantitatively reproduced this effect, allowed separation of initial- and final-state contributions, and provided an explanation in terms of a roughly constant charge transfer per O atom. We have now conducted similar measurements and calculations for three well-defined adsorbate and coadsorbate layers containing O and H atoms: (1 × 1)-H, (2 × 2)-(O+H) and (2 × 2)-(O+3H) on Ru(0001). As H is stabilized in fcc sites in the prior two structures and in hcp sites in the latter, this enables us to not only study coverage and coadsorption effects on the adsorbate-induced SCLSs, but also the sensitivity to similar adsorption sites. Remarkably good agreement is obtained between experiment and calculations for the energies and geometries of the layers, as well as for all aspects of the SCLS values. The additivity of the next-neighbor adsorbate-induced SCLSs is found to prevail even for the coadsorbate structures. While this confirms the suggested use of SCLSs as fingerprints of the adsorbate configuration, their sensitivity is further demonstrated by the slightly different shifts unambiguously determined for H adsorption in either fcc or hcp hollow sites.
The role of dissolved oxygen in supercritical water in the oxidation of ferritic–martensitic steel
Abstract To assess the role of dissolved oxygen in supercritical water on the growth processes of oxide scales, a marker experiment of ferritic–martensitic steel was performed by exposing to supercritical water (H 2 16 O) containing marked 18 O 2 at 600 °C under 25 MPa. The oxide scale was analysed by using Secondary Ion Mass Spectrometry (SIMS). The oxygen isotope profile shows that dissolved oxygen and supercritical water react with metals simultaneously. Dissolved oxygen changes the oxidation/reduction potential of supercritical water leading to an increase in the oxidation rate. The oxidation rate increases with increase in dissolved oxygen content in supercritical water. The mechanism of the effect of dissolved oxygen on oxidation is discussed.