Stability of Iridium Single Atoms on Fe₃O₄(001) in the mbar Pressure Range

Stable single metal adatoms on oxide surfaces are of great interest for future applications in the field of catalysis. We studied iridium single atoms (Ir₁) supported on a Fe₃O₄(001) single crystal, a model system previously only studied in ultra-high vacuum, to explore their behavior upon exposure to several gases in the millibar range (up to 20 mbar) utilizing ambient-pressure X-ray photoelectron spectroscopy. The Ir₁ single adatoms appear stable upon exposure to a variety of common gases at room temperature, including oxygen (O₂), hydrogen (H₂), nitrogen (N₂), carbon monoxide (CO), argon (Ar), and water vapor. Changes in the Ir 4f binding energy suggest that Ir₁ interacts not only with adsorbed and dissociated molecules but also with water/OH groups and adventitious carbon species deposited inevitably under these pressure conditions. At higher temperatures (473 K), iridium adatom encapsulation takes place in an oxidizing environment (a partial O₂ pressure of 0.1 mbar). We attribute this phenomenon to magnetite growth caused by the enhanced diffusion of iron cations near the surface. These findings provide an initial understanding of the behavior of single atoms on metal oxides outside the UHV regime.