Theoretical Study on Pt1/CeO2 Single Atom Catalysts for CO Oxidation

Understanding the influence of structural configurations on catalytic performance is crucial for optimizing atom‐efficient single‐atom catalysts (SACs). In this study, we conducted a density functional theory (DFT) investigation of single Pt atoms positioned at step‐edges and within a solid solution on the CeO2(111) surface. We compared these configurations in terms of thermodynamic stability, electronic properties, and further potential energy surfaces for CO oxidation. Stability studies revealed that the solid solution catalyst exhibits greater stability compared to the step‐edge catalyst. Additionally, the Pt in the solid solution catalyst can effectively activate lattice oxygen atoms, making the catalyst more conducive to the formation of oxygen vacancies. The CO oxidation process was analyzed using the Mars‐van Krevelen mechanism, revealing that the solid solution catalyst possesses a more moderate CO adsorption energy. This, coupled with its lower oxygen vacancy formation energy, leads to reduced energy barriers throughout the CO oxidation cycle. Our findings highlight the strong dependence of catalytic activity on the specific configuration of Pt atoms within the CeO2 matrix, with the solid solution model demonstrating superior catalytic efficiency compared to the step‐edge‐supported Pt catalysts.