Platinum-Iron(II) Oxide Sites Directly Responsible for Preferential Carbon Monoxide Oxidation at Ambient Temperature:...

Operando X-ray absorption spectroscopy identified that the concentration of Fe²⁺ species in the working state-of-the-art Pt-FeO_x catalysts quantitatively correlates to their preferential carbon monoxide oxidation steady-state reaction rate at ambient temperature. Deactivation of such catalysts with time on stream originates from irreversible oxidation of active Fe²⁺ sites. The active Fe²⁺ species are presumably Fe⁺² O^-2 clusters in contact with platinum nanoparticles; they coexist with spectator trivalent oxidic iron (Fe³⁺ ) and metallic iron (Fe⁰ ) partially alloyed with platinum. The concentration of active sites and, therefore, the catalyst activity strongly depends on the pretreatment conditions. Fe²⁺ is the resting state of the active sites in the preferential carbon monoxide oxidation cycle.