An Atomic-Scale View of CO and H-2 Oxidation on a Pt/Fe3O4 Model Catalyst

Metal-support interactions are frequently invoked to explain the enhanced catalytic activity of metal nanoparticles dispersed over reducible metal oxide supports, yet the atomic-scale mechanisms are rarely known. In this report, scanning tunneling microscopy was used to study a Pt1-6/Fe3O4 model catalyst exposed to CO, H-2, O-2, and mixtures thereof at 550 K. CO extracts lattice oxygen atoms at the cluster perimeter to form CO2, creating large holes in the metal oxide surface. H-2 and O-2 dissociate on the metal clusters and spill over onto the support. The former creates surface hydroxy groups, which react with the support, ultimately leading to the desorption of water, while oxygen atoms react with Fe from the bulk to create new Fe3O4(001) islands. The presence of the Pt is crucial because it catalyzes reactions that already occur on the bare iron oxide surface, but only at higher temperatures.