DFT insights into oxygen vacancy formation and chemical looping dry reforming of methane on metal-substituted CeO₂ (111) surface

Abstract

The oxygen vacancy formation energy and chemical looping dry reforming of methane over metal-substituted CeO₂ (111) are investigated based on density functional theory calculations. The calculated results indicate that among the various metals that can substitute for the Ce atom in the CeO₂(111) surface, Zn substitution results in the lowest oxygen vacancy formation energy. For the activation of CH₄ on CeO₂ (111) and Zn-substituted CeO₂ (111) surfaces, the calculated results illustrate that the dissociation process of CH_3(ads) is very difficult on pristine surfaces and unfavorable for CHO_(ads) on substituted surfaces. Furthermore, the dissociative adsorption of CO and H₂ on the Zn-substituted CeO₂ (111) surface requires high energy, which is unfavorable for syngas production. This work demonstrates that excessive formation of oxygen vacancy can lead to excessively high adsorption energies, thus limiting the conversion efficiency of the reaction intermediates. This finding provides important guidance and application prospects for the design and optimization of oxygen carrier materials, especially in the field of chemical looping dry methane reforming to syngas.

Graphical abstract

Keywords

Zn-substituted / CeO₂ (111) / oxygen vacancy formation / chemical looping dry reforming of methane / density functional theory

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Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Grant Nos. 52466006, U2202251 and 52174279), Yunnan Fundamental Research Projects (Grant Nos. 202301AU070027 and 202401AT070388), Major R&D Special Project of Yunnan Province “Research and Application of Catalytic Conversion of CO₂ to High Value Chemicals” (Grant No. 202302AG050005), Applied Basic Research Program of Yunnan Province for Distinguished Young Scholars (Grant No. 202201AV070004), Central Guiding Local Science and Technology Development Fund (Grant No. 202207AA110001) and the Analysis Test Fund of Kunming University of Science and Technology (Grant No. 2023T20210207).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2513-2 and is accessible for authorized users.

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