RESUMEN
This work reports about a novel approach for investigating surface processes during the early stages of galvanic corrosion of stainless steelin situby employing ultra-thin films and synchrotron x-radiation. Characterized by x-ray techniques and voltammetry, such films, sputter deposited from austenitic steel, were found representing useful replicas of the target material. Typical for stainless steel, the surface consists of a passivation layer of Fe- and Cr-oxides, a couple of nm thick, that is depleted of Ni. Films of ≈4 nm thickness were studiedin situin an electrochemical cell under potential control (-0.6 to +0.8 V vs Ag/AgCl) during exposure to 0.1 M KCl. Material transport was recorded with better than 1/10 monolayer sensitivity by x-ray spectroscopy. Leaching of Fe was observed in the cathodic range and the therefor necessary reduction of Fe-oxide appears to be accelerated by atomic hydrogen. Except for minor leaching, reduction of Ni, while expected from Pourbaix diagram, was not observed until at a potential of about +0.8 V Cr-oxide was removed from the steel film. After couple of minutes exposure at +0.8 V, the current in the electrochemical cell revealed a rapid pitting event that was simultaneously monitored by x-ray spectroscopy. Continuous loss of Cr and Ni was observed during the induction time leading to the pitting, suggesting a causal connection with the event. Finally, a spectroscopic image of a pit was recordedex situwith 50 nm lateral and 1 nm depth resolution by soft x-ray scanning absorption microscopy at the Fe L2,3-edges by using a 80 nm film on a SiN membrane, which is further demonstrating the usefulness of thin films for corrosion studies.
RESUMEN
The carbon-carbon coupling via electrochemical reduction of carbon dioxide represents the biggest challenge for using this route as platform for chemicals synthesis. Here we show that nanostructured iron (III) oxyhydroxide on nitrogen-doped carbon enables high Faraday efficiency (97.4%) and selectivity to acetic acid (61%) at very-low potential (-0.5 V vs silver/silver chloride). Using a combination of electron microscopy, operando X-ray spectroscopy techniques and density functional theory simulations, we correlate the activity to acetic acid at this potential to the formation of nitrogen-coordinated iron (II) sites as single atoms or polyatomic species at the interface between iron oxyhydroxide and the nitrogen-doped carbon. The evolution of hydrogen is correlated to the formation of metallic iron and observed as dominant reaction path over iron oxyhydroxide on oxygen-doped carbon in the overall range of negative potential investigated, whereas over iron oxyhydroxide on nitrogen-doped carbon it becomes important only at more negative potentials.