Single-atom catalysts maximize the utilization of supported precious metals by exposing every single metal atom to reactants. To avoid sintering and deactivation at realistic reaction conditions, single metal atoms are stabilized by specific adsorption sites on catalyst substrates. Here we show by combining photoelectron spectroscopy, scanning tunnelling microscopy and density functional theory calculations that Pt single atoms on ceria are stabilized by the most ubiquitous defects on solid surfaces—monoatomic step edges. Pt segregation at steps leads to stable dispersions of single Pt²⁺ ions in planar PtO₄ moieties incorporating excess O atoms and contributing to oxygen storage capacity of ceria. We experimentally control the step density on our samples, to maximize the coverage of monodispersed Pt²⁺ and demonstrate that step engineering and step decoration represent effective strategies for understanding and design of new single-atom catalysts.

The concept of single atom catalysis offers maximum noble metal efficiency for the development of low-cost catalytic materials. Among possible applications are catalytic materials for proton exchange membrane fuel cells. In the present review, recent efforts towards the fabrication of single atom catalysts on nanostructured ceria and their reactivity are discussed in the prospect of their employment as anode catalysts. The remarkable performance and the durability of the ceria-based anode catalysts with ultra-low Pt loading result from the interplay between two states associated with supported atomically dispersed Pt and sub-nanometer Pt particles. The occurrence of these two states is a consequence of strong interactions between Pt and nanostructured ceria that yield atomically dispersed species under oxidizing conditions and sub-nanometer Pt particles under reducing conditions. The square-planar arrangement of four O atoms on {100} nanoterraces has been identified as the key structural element on the surface of the nanostructured ceria where Pt is anchored in the form of Pt²⁺ species. The conversion of Pt²⁺ species to sub-nanometer Pt particles is triggered by a redox process involving Ce³⁺ centers. The latter emerge due to either oxygen vacancies or adsorption of reducing agents. The unique properties of the sub-nanometer Pt particles arise from metal–support interactions involving charge transfer, structural flexibility, and spillover phenomena. The abundance of specific adsorption sites similar to those on {100} nanoterraces determines the ideal (maximum) Pt loading in Pt–CeO_x films that still allows reversible switching between the atomically dispersed Pt and sub-nanometer particles yielding high activity and durability during fuel cell operation.