Insights into the Structural Dynamics of Pt/CeO$_{2}$ Single-Site Catalysts during CO Oxidation

Despite their high atomic dispersion, single site catalysts with Pt supported on CeO$_{2}$ were found to have a low activity during oxidation reactions. In this study, we report the behavior of Pt/CeO$_{2}$ single site catalyst under more complex gas mixtures, including CO, C$_{3}$H$_{6}$ and CO/C$_{3}$H$_{6}$ oxidation in the absence or presence of water. Our systematic operando high-energy resolution-fluorescence-detected X-ray absorption near-edge structure (HERFD-XANES) spectroscopic study combined with multivariate curve resolution with alternating least squares (MCR-ALS) analysis identified five distinct states in the Pt single site structure during CO oxidation light-off. After desorption of oxygen and autoreduction of Pt$^{4+}$ to Pt$^{2+}$ due to the increase of temperature, CO adsorbs and reduces Pt$^{2+}$ to Pt$^{δ+}$ and assists its migration with final formation of Pt$_{x^Δ+}$ clusters. The derived structure–activity relationships indicate that partial reduction of Pt single sites is not sufficient to initiate the conversion of CO. The reaction proceeds only after the regrouping of several noble metal atoms in small clusters, as these entities are probably able to influence the mobility of the oxygen at the interface with ceria.