Uniformity Is Key in Defining Structure-Function Relationships for Atomically Dispersed Metal Catalysts: The Case of...

Catalysts consisting of atomically dispersed Pt (Pt_iso) species on CeO₂ supports have received recent interest due to their potential for efficient metal utilization in catalytic convertors. However, discrepancies exist between the behavior (reducibility, interaction strength with adsorbates) of high surface area Pt_iso/CeO₂ systems and of well-defined surface science and computational model systems, suggesting differences in Pt local coordination in the two classes of materials. Here, we reconcile these differences by demonstrating that high surface area Pt_iso/CeO₂ synthesized at low Pt loadings (<0.1% weight) exhibit resistance to reduction and sintering up to 500 °C in 0.05 bar H₂ and minimal interactions with CO-properties previously seen only for model system studies. Alternatively, Pt loadings >0.1 weight % produce a distribution of sub-nanometer Pt structures, which are difficult to distinguish using common characterization techniques, and exhibit strong interactions with CO and weak resistance to sintering, even in 0.05 bar H₂ at 50 °C-properties previously seen for high surface area materials. This work demonstrates that low metal loadings can be used to selectively populate the most thermodynamically stable adsorption sites on high surface area supports with atomically dispersed metals. Further, the site uniformity afforded by this synthetic approach is critical for the development of relationships between atomic scale local coordination and functional properties. Comparisons to recent studies of Pt_iso/TiO₂ suggest a general compromise between the stability of atomically dispersed metal catalysts and their ability to interact with and activate molecular species.