Interfacial Charge Transfer between Phenyl-Capped Aniline Tetramer Films and Iron Oxide Surfaces

Redox-active organic compounds have been studied as corrosion inhibitors for steel. Even though it is clear that chemical interactions at the organic–metal oxide interface are behind this inhibitive process, the detailed mechanism is not yet fully understood. Using phenyl-capped aniline tetramer (PCAT), we have elucidated the interactions at the interface with iron oxide. We demonstrate the partial reduction of fully oxidized PCAT and the partial oxidation of fully reduced PCAT upon interaction with iron oxide. X-ray photoelectron spectroscopy reveals the appearance of charged nitrogen structures in PCAT deposited on hematite. Iron oxide films in contact with reduced PCAT show a higher conductance due to the introduction of defects, resulting in n-doping. In contrast, the iron oxide film in contact with oxidized PCAT shows a lower conductance, indicating that defects in the film are removed via oxidation, thus reducing the doping level. This is consistent with accepted models for corrosion inhibition, in which PCAT assists in the formation of a passive oxide film. These results are indicative of interfacial charge transfer between PCAT and iron oxide. The extent of the charge transfer and the direction of redox processes depend on the oxidation state of the molecules, enabling the construction of redox-active devices, including sensors and switches.