Oxygen vacancy enhanced oxidative dehydrogenation of propane with carbon dioxide over PtSn/Ce_1−xLa_xO_2−δ

Abstract

Supported Pt-based catalysts are promising for the oxidative dehydrogenation of propane with CO₂ (CO₂-ODP), which is regarded as an attractive process for simultaneous propene production and CO₂ reduction to CO. By incorporating La³⁺ into CeO₂, we found that the performance of PtSn/Ce_1−xLa_xO_2−δ (x = 0, 0.05, 0.1, and 0.3) for CO₂-ODP is enhanced. Specifically, the propene yield over PtSn/CeO₂ dropped sharply from 17% to 3% after 21.83 h on stream. In contrast, the optimized PtSn/Ce_0.9La_0.1O_2−δ catalyst maintained a much higher propene yield, declining only slightly from 23% to 20%, confirming that La incorporation markedly enhances both activity and stability. Complementary characterization results demonstrate that doping low-valent La³⁺ into CeO₂ increases oxygen vacancies via charge compensation, strengthening the Pt–O bond within the Pt–O–Ce interface. This preferentially activates C–H bonds in propane while suppressing C–C scission, thereby increasing propene yield. Meanwhile, the increased oxygen vacancies accelerate CO₂ activation, sustaining the redox cycle and thus improving the catalyst stability. Owing to these synergistic effects, PtSn/Ce_0.9La_0.1O_2−δ exhibits excellent catalytic performance, outperforming most reported Pt-based catalysts. These findings highlight that tuning oxygen vacancies at the metal-support interface is a promising strategy for developing efficient CO₂-ODP catalysts.

Graphical abstract

Keywords

propane / oxidative dehydrogenation / carbon dioxide / supported PtSn / lanthanum-doped ceria

References

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