Temperature-driven mechanistic transition in propylene oxidation over Pt/CeO2 ensemble catalysts

Zihao Li; Xingyan Chen; Yao Lv; Sheng Dai; Huazhen Chang; Zhenguo Li; Kailong Ye; Fudong Liu; Lei Ma; Naiqiang Yan

doi:10.1038/s41467-025-64243-y

Temperature-driven mechanistic transition in propylene oxidation over Pt/CeO₂ ensemble catalysts

Zihao Li, Xingyan Chen, Yao Lv, Sheng Dai, Huazhen Chang, Zhenguo Li, Kailong Ye, Fudong Liu, Lei Ma, Naiqiang Yan

Research output: Contribution to journal › Article › peer-review

Abstract

Pt/CeO₂ ensemble catalysts are promising for propylene (C₃H₆) 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 H₂-activated Pt/CeO₂ 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 sp³ C-H bonds is the rate-determining step. At low temperatures, both C₃H₆ and O₂ adsorb and activate on metallic Pt, without CeO₂ involvement. Once the temperature exceeds threshold, C₃H₆ fully covers Pt sites, while O₂ 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 C₃H₆ oxidation.

Original language	English
Article number	9199
Journal	Nature Communications
Volume	16
Issue number	1
DOIs	https://doi.org/10.1038/s41467-025-64243-y
State	Published - Dec 2025
Externally published	Yes

Funding

L.M. acknowledges the financial support by the National Key Research and Development Program of China (2024YFB4105100), the National Natural Science Foundation of China (22176122), the Shanghai Pujiang Program (20PJ1407000), the Oceanic Interdisciplinary Program of Shanghai Jiao Tong University (SL2022ZD104), and the Zhejiang Key Laboratory of Low-carbon Control Technology for Industrial Pollution, Zhejiang University of Technology (2025DTZL01 and 2025ZY01076). S.D. was supported by the National Natural Science Foundation of China (22376062) and the Science and Technology Commission of Shanghai Municipality (24DX1400200 and 22ZR1415700). H.C. was supported by the National Natural Science Foundation of China (22176217) and the National Engineering Laboratory for Mobile Source Emission Control Technology (NELMS2018A12). F.L. thanks the Startup Fund from the University of California, Riverside (UCR).

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title = "Temperature-driven mechanistic transition in propylene oxidation over Pt/CeO2 ensemble catalysts",

abstract = "Pt/CeO2 ensemble catalysts are promising for propylene (C3H6) 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 H2-activated Pt/CeO2 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 sp3 C-H bonds is the rate-determining step. At low temperatures, both C3H6 and O2 adsorb and activate on metallic Pt, without CeO2 involvement. Once the temperature exceeds threshold, C3H6 fully covers Pt sites, while O2 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 C3H6 oxidation.",

author = "Zihao Li and Xingyan Chen and Yao Lv and Sheng Dai and Huazhen Chang and Zhenguo Li and Kailong Ye and Fudong Liu and Lei Ma and Naiqiang Yan",

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T1 - Temperature-driven mechanistic transition in propylene oxidation over Pt/CeO2 ensemble catalysts

AU - Li, Zihao

AU - Chen, Xingyan

AU - Lv, Yao

AU - Dai, Sheng

AU - Chang, Huazhen

AU - Li, Zhenguo

AU - Ye, Kailong

AU - Liu, Fudong

AU - Ma, Lei

AU - Yan, Naiqiang

PY - 2025/12

Y1 - 2025/12

N2 - Pt/CeO2 ensemble catalysts are promising for propylene (C3H6) 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 H2-activated Pt/CeO2 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 sp3 C-H bonds is the rate-determining step. At low temperatures, both C3H6 and O2 adsorb and activate on metallic Pt, without CeO2 involvement. Once the temperature exceeds threshold, C3H6 fully covers Pt sites, while O2 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 C3H6 oxidation.

AB - Pt/CeO2 ensemble catalysts are promising for propylene (C3H6) 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 H2-activated Pt/CeO2 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 sp3 C-H bonds is the rate-determining step. At low temperatures, both C3H6 and O2 adsorb and activate on metallic Pt, without CeO2 involvement. Once the temperature exceeds threshold, C3H6 fully covers Pt sites, while O2 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 C3H6 oxidation.

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SN - 2041-1723

VL - 16

JO - Nature Communications

JF - Nature Communications

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ER -

Temperature-driven mechanistic transition in propylene oxidation over Pt/CeO₂ ensemble catalysts

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