Transformation of Highly Stable Pt Single Sites on Defect Engineered Ceria into Robust Pt Clusters for Vehicle Emission Control

Engineering surface defects on metal oxide supports could help promote the dispersion of active sites and catalytic performance of supported catalysts. Herein, a strategy of ZrO₂ doping was proposed to create rich surface defects on CeO₂ (CZO) and, with these defects, to improve Pt dispersion and enhance its affinity as single sites to the CZO support (Pt/CZO). The strongly anchored Pt single sites on CZO support were initially not efficient for catalytic oxidation of CO/C₃H₆. However, after a simple activation by H₂ reduction, the catalytic oxidation performance over Pt/CZO catalyst was significantly boosted and better than Pt/CeO₂. Pt/CZO catalyst also exhibited much higher thermal stability. The structural evolution of Pt active sites by H₂ treatment was systematically investigated on aged Pt/CZO and Pt/CeO₂ catalysts. With H₂ reduction, ionic Pt single sites were transformed into active Pt clusters. Much smaller Pt clusters were created on CZO (ca. 1.2 nm) than on CeO₂ (ca. 1.8 nm) due to stronger Pt-CeO₂ interaction on aged Pt/CZO. Consequently, more exposed active Pt sites were obtained on the smaller clusters surrounded by more oxygen defects and Ce³⁺ species, which directly translated to the higher catalytic oxidation performance of activated Pt/CZO catalyst in vehicle emission control applications.