Investigation of N adsorption on FeO(001) using ambient pressure X-ray photoelectron spectroscopy and density functional theory.

Reactions on iron oxide surfaces are prevalent in various chemical processes from heterogeneous catalysts to minerals. Nitrogen (N) is known to dissociate on iron surfaces, a precursor for ammonia production in the Haber-Bosch process, where the dissociation of N is the limiting step in the reaction under equilibrium conditions. However, little is known about N adsorption on other iron-based materials, such as iron oxide surfaces that are ubiquitous in soils, steel pipelines, and other industrial materials. An atomistic description is reported for the binding of N on the FeO(001) surface using first principles calculations with ambient pressure X-ray photoelectron spectroscopy. Two primary adsorption sites are experimentally identified from N dissociation on FeO(001). The electronic signatures associated with the valence band region unambiguously show how the electronic structure of magnetite transforms near ambient pressures due to the binding of atomic nitrogen to different surface sites. Overall, the experimental and theoretical results of our study bridge the gap between ultra-high vacuum studies and reaction conditions to provide insight into other nitrogen-based chemistry on iron oxide surfaces that impact the agriculture and energy industries.