The role of polaronic states in the enhancement of CO oxidation by single-atom Pt/CeO2

Journal article, 2023

Single Atom Catalysts (SACs) have shown that the miniaturization of the active site implies new phenomena like dynamic charge transfer between isolated metal atoms and the oxide. To obtain direct proof of this character is challenging, as many experimental techniques provide averaged properties or have limitations with poorly conductive materials, leaving kinetic measurements from catalytic testing as the only reliable reference. Here we present an integrated Density Functional Theory-Microkinetic model including ground and metastable states to address the reactivity of Pt1/CeO2 for CO oxidation. Our results agree with experimentally available kinetic data in the literature and show that CO oxidation activity of Pt1/CeO2 is tunable via the electronic properties of the support. Particularly, samples with higher n-doping via oxygen depletion should be better in CO oxidation, as they help maintain the active state Pt0 of the catalyst. This provides an alternative strategy for tuning the performance of low-temperature oxidations in single-atom catalysts via charge transfer control.