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CO2 hydrogenation to methane over Ni/ZrO2 and Ni/CeO2 catalysts: experimental and DFT studies

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Abstract

In this paper, performance of ZrO2 and CeO2 supported Ni catalysts on CO2 hydrogenation reaction was investigated in continuous flow reactor. The results revealed that Ni/ZrO2 catalyst exhibited superior performance compared to Ni/CeO2, with a CO2 conversion rate of 71.84%, a CH4 formation rate of 21.03 mmol g−1 h−1, and excellent reaction stability at 400 °C. And the activation energy of Ni/ZrO2 was lower than that of Ni/CeO2. N2 adsorption–desorption, SEM, XRD, XPS, CO2-TPD and O2-TPO analysis results suggest that Ni/ZrO2 is a multi-stage pore material, which has slit holes formed by the accumulation of sheet-like particles, as well as a superior dispersion of Ni on ZrO2. Moreover, Ni/ZrO2 shows higher alkalinity and remarkable resistance to carbon accumulation. DFT calculations demonstrated that CO2 can be more easily adsorbed on ZrO2 surface, and one O-terminus of CO2 is closer to top sites of ZrO2, which is favorable for electron transfer and promotes the activation of CO2.

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Acknowledgements

The work was supported by National Key Research and Development Program of China (2022YFE0206600), Sichuan Science and Technology Program (2023YFSY0034) and Xi'an Jiaotong University Fund (xjh012020008). We thank technicians at Instrument Analysis Center of Xi'an Jiaotong University for their assistance with XRD, SEM, etc. The work was carried out at Shanxi Supercomputing Center of China, and the calculation were performed on TianHe-2.

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  1. Dan Li and Xin Ding have contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory of Thermo-Fluid Science and Engineering, Ministry of Education, School of Energy and Power Engineering, Xi’an Jiaotong University, Xi’an, 710049, Shaanxi, People’s Republic of China

    Dan Li, Xin Ding, Xu Liu, Jiahui Cheng & Yang Guo

  2. School of Chemical Engineering and Technology, Xi’an Jiaotong University, Xi’an, 710049, Shaanxi, People’s Republic of China

    Zhao Jiang

  3. Sichuan Digital Economy Industry Development Research Institute, Chengdu, 610036, Sichuan, People’s Republic of China

    Dan Li, Xin Ding, Xu Liu, Jiahui Cheng, Zhao Jiang & Yang Guo

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Contributions

DL and XD contributed equally to this work on the determination of article structure, information collection, manuscript writing and revision. JC helped to search for literatures and write manuscript. ZJ did DFT calculation and drafted result in the article. YG gave many useful suggestions about topic selection and manuscript writing.

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Correspondence to Yang Guo.

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Li, D., Ding, X., Liu, X. et al. CO2 hydrogenation to methane over Ni/ZrO2 and Ni/CeO2 catalysts: experimental and DFT studies. J Mater Sci 58, 12584–12595 (2023). https://doi.org/10.1007/s10853-023-08814-8

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