Temperature-driven mechanistic transition in propylene oxidation over Pt/CeO<sub>2</sub> ensemble catalysts.

Li, Zihao; Chen, Xingyan; Lv, Yao; Dai, Sheng; Chang, Huazhen; Li, Zhenguo; Ye, Kailong; Liu, Fudong et al. · Nat Commun · 2025

basic_science · Level V

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Abstract

Pt/CeO<sub>2</sub> ensemble catalysts are promising for propylene (C<sub>3</sub>H<sub>6</sub>) oxidation in vehicle exhaust, yet identifying the intrinsic active sites and understanding how the metal-support interface evolves at varying reaction temperatures remains contentious. Herein, we demonstrate that H<sub>2</sub>-activated Pt/CeO<sub>2</sub> ensemble catalysts feature metallic Pt ensembles as intrinsic active sites, lowering the 50% conversion temperature by 120 °C after hydrogen activation. Various operando characterization techniques reveal an approximately 170 °C threshold temperature for the dynamic change of the reaction models. Meanwhile, kinetics and theoretical analysis illustrates that oxygen-facilitated dehydrogenation of sp<sup>3</sup> C-H bonds is the rate-determining step. At low temperatures, both C<sub>3</sub>H<sub>6</sub> and O<sub>2</sub> adsorb and activate on metallic Pt, without CeO<sub>2</sub> involvement. Once the temperature exceeds threshold, C<sub>3</sub>H<sub>6</sub> fully covers Pt sites, while O<sub>2</sub> activates over Pt-O-Ce interfaces and participates in dehydrogenation. This study highlights the dynamic nature of oxygen activation, leading to distinct reaction temperature regimes during C<sub>3</sub>H<sub>6</sub> oxidation.