Core-shell Pd@CeO2/γ‐Al2O3 catalysts: Boosting efficiency and durability in stoichiometric natural gas vehicle exhaust treatment

doi:10.1016/S1872-2067(25)64926-6

Chinese Journal of Catalysis ›› 2026, Vol. 82: 348-362.DOI: 10.1016/S1872-2067(25)64926-6

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Core-shell Pd@CeO₂/γ‐Al₂O₃ catalysts: Boosting efficiency and durability in stoichiometric natural gas vehicle exhaust treatment

Run Pan^a^,^g^,¹, Abubakar Yusuf^a^,¹, Chengjun Wang^b^,^*(), Jianrong Li^c, Zhiyu Xiao^a, Shuai Liu^d, Yidong Zhong^a, Yong Ren^e, Zheng Wang^a, Hainam Do^a, John L. Zhou^a^,^*(), George Zheng Chen^f, Jun He^a^,^g^,^*()

^aDepartment of Chemical and Environmental Engineering, University of Nottingham Ningbo China, Ningbo 315000, Zhejiang, China
^bSchool of Chemical and Environmental Engineering, Hunan Institute of Technology, Hengyang 421000, Hunan, China
^cNingbo Key Laboratory of Urban Environmental Pollution and Control, Ningbo (Beilun) Zhongke Haixi Industrial Technology Innovation Center, Ningbo 315000, Zhejiang, China
^dSchool of Mechatronics and Energy Engineering, NingboTech University, Ningbo 315000, Zhejiang, China
^eDepartment of Mechanical, Materials and Manufacturing Engineering, University of Nottingham Ningbo China, Ningbo 315000, Zhejiang, China
^fDepartment of Chemical and Environmental Engineering, Faculty of Engineering, University of Nottingham, Nottingham, UK
^gNottingham Ningbo China Beacons of Excellence Research and Innovation Institute, Ningbo 315000, Zhejiang, China

Received:2025-07-23 Accepted:2025-10-21 Online:2026-03-18 Published:2026-03-05
Contact: * E-mail: cjwang@hnit.edu.cn (C. Wang),john.zhou@nottingham.edu.cn (J. L. Zhou),jun.he@nottingham.edu.cn (J. He).
About author:¹Contributed equally to this work.
Supported by:
Ningbo Natural Science Foundation Grant(2023J024);Ningbo Commonweal Key Research Program(2023S038);Ningbo Key Technology Breakthrough Projects under Yongjiang Science and Innovation 2035 Scheme(2024Z237);Ningbo Key Technology Breakthrough Projects under Yongjiang Science and Innovation 2035 Scheme(2024Z251);Hunan Provincial Natural Science Foundation of China(2025JJ50204)

Abstract

Abstract:

Natural gas vehicles (NGVs) offer significant environmental advantages by reducing pollutant emissions, but effective exhaust treatment remains a challenge due to high methane emissions and catalyst deactivation over time. This study introduces a core-shell Pd@CeO₂/Al₂O₃ three-way catalyst (TWC) designed to enhance the efficiency and durability of NGV exhaust treatment. The core-shell structure significantly improves catalytic performance. The optimized Pd@Ce/Al (S-500) catalyst demonstrates excellent low-temperature activity, with T₅₀ values of 336 °C for CH₄ and 397 °C for NO. It also achieves remarkable reductions of 113 and 177 °C in the T₉₀ for CH₄ and NO conversion, respectively, compared to the non-core-shell counterpart, Pd-Ce/Al (S-500). Characterizations reveal enhanced metal-support interactions, increased oxygen vacancies, and optimized Pd-CeO₂ interfaces as key active sites. Density functional theory calculations further demonstrate that the core-shell structure facilitates electron transfer at Pd-CeO₂ interfaces and lowers energy barriers for three-way reactions, enhancing catalytic efficiency. Notably, the core-shell Pd@Ce/Al (S-500) catalyst maintains high conversion efficiency for CH₄ and NO, with only slight losses (5.5% and 6.6%, respectively) over a 100-h time-on-stream stability test, following 16 h of harsh hydrothermal aging at 800 °C, showcasing its long-term stability. These findings provide a deeper understanding of the role of the core-shell Pd@CeO₂ structure in Pd-based TWCs and offer valuable insights for designing durable and efficient catalysts to meet the stringent emission standards of NGVs.

Key words: Core-shell catalyst, Pd@CeO₂/Al₂O₃, Natural gas vehicles, Stoichiometric combustion, Three-way catalysis, Hydrothermal stability

Run Pan, Abubakar Yusuf, Chengjun Wang, Jianrong Li, Zhiyu Xiao, Shuai Liu, Yidong Zhong, Yong Ren, Zheng Wang, Hainam Do, John L. Zhou, George Zheng Chen, Jun He. Core-shell Pd@CeO₂/γ‐Al₂O₃ catalysts: Boosting efficiency and durability in stoichiometric natural gas vehicle exhaust treatment[J]. Chinese Journal of Catalysis, 2026, 82: 348-362.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64926-6

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Figures/Tables 6

Fig. 1. TEM images of Pd@CeO2 (A1,A2), Pd@CeO2-OA (B1, B2), Pd-CeO2 (C1,C2), Pd-CeO2-OA (D1,D2). DF-TEM images with EDS mapping analysis and EDS line profiles of Pd@CeO2 (E1-E4) and Pd@CeO2-OA (F1-F4).

Fig. 2. Heating light-off curves of all samples on catalytic CO, CH4 and NO reaction and the samples calcined at 500 °C (a-c) and 850 °C (d-f). Conditions: 5000 ppm CO, 1000 ppm CH4, 1000 ppm NO, 4000 ppm O2, 10% CO2 and N2, GHSV = 100 L/(g·h). (g-i) TOS test on catalytic CO, CH4 and NO reaction for aged Pd@Ce/Al (S-500) and aged Pd-Ce/Al (S-500) at GHSV = 100 L/(g·h) and 450 °C. Conditions: 5000 ppm CO, 1000 ppm CH4, 1000 ppm NO, 4000 ppm O2, 10% CO2, 10% H2O and N2.

Fig. 3. Arrhenius plots for CH4 over the Pd@Ce/Al-E, Pd@Ce/Al-S, Pd-Ce/Al-E and Pd-Ce/Al-S calcined at 500 °C (a) and 850 °C (b). Conditions: 5000 ppm CO, 1000 ppm CH4, 1000 ppm NO, 4000 ppm O2, 10% CO2 and N2, GHSV = 300 L/(g·h).

Fig. 4. XPS spectra of Pd 3d (a,b), O 1s (c,d) and Ce 3d (e,f) of catalysts.

Fig. 5. H2-TPR profiles (a,b) and DRIFTS spectra (c,d) of Pd@Ce/Al-E, Pd@Ce/Al-S, Pd-Ce/Al-E and Pd-Ce/Al-S calcined at 500 and 850 °C.

Fig. 6. (a) Partial density of states for PdO (101) and PdCeO (111). The energy profile on PdO (101) (red) and PdCeO (111) (black) of CH4 dissociation (b), NO + CO reaction (c), NO + CH4 reaction (d), NO dissociation (e), and H2O dissociation (f). O: red; Ce: yellow; Pd: gray; C: brown; H: pink.

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Core-shell Pd@CeO₂/γ‐Al₂O₃ catalysts: Boosting efficiency and durability in stoichiometric natural gas vehicle exhaust treatment

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