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Nano Research 2022, 15(7): 5831-5841 https://doi.org/10.1007/s12274-022-4207-8
Research Article | Issue | Published: 18 April 2022

Identifying the roles of Ce3+–OH and Ce–H in the reverse water–gas shift reaction over highly active Ni-doped CeO2 catalyst

Show Author's Information Haidong Shen1,  Yujuan Dong1,  Shaowei Yang1,  Yuan He1,  Qimeng Wang1,  Yueling Cao1,  Wenbin Wang1,  Tianshuai Wang1( ),  Qiuyu Zhang1( ),  Hepeng Zhang1,2( )
Xi’an Key Laboratory of Functional Organic Porous Materials, School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi’an 710129, China
Research & Development Institute of Northwestern Polytechnical University in Shenzhen, Shenzhen 518057, China
Keywords:
CO2 hydrogenation , Ni-doped CeO2, cerium hydride, mechanism investigation, reverse water–gas shift (RWGS) reaction
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Catalysts
Cite this article:
Shen H, Dong Y, Yang S, et al. Identifying the roles of Ce3+–OH and Ce–H in the reverse water–gas shift reaction over highly active Ni-doped CeO2 catalyst. Nano Research, 2022, 15(7): 5831-5841. https://doi.org/10.1007/s12274-022-4207-8
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Abstract Full text Electronic supplementary material About this article

Nickel-CeO2-based materials are commonly used for the thermal catalytic hydrogenation of CO2. However, high Ni loadings and low CO selectivity restrict their use in the reverse water–gas shift (RWGS) reaction. Herein, we demonstrate a highly active, robust, and low-Ni-doped (1.1 wt.%) CeO2 catalyst (1.0-Ni-CeO2). The Ni-based-mass-specific CO formation rate reaches up to 1,542 mmol·gNi−1·h−1 with 100% CO selectivity at 300 °C for 100 h, among the best values reported in the literature. Density functional theory (DFT) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) results reveal that the enhanced catalytic activity is attributed to the abundant Ce–H species, while the high selectivity results from low CO affinity. More importantly, a new reaction mechanism is proposed, which involves the reduction of bicarbonate to generate formate intermediate and CO by the H− released from Ce–H species. The new findings in this work will benefit the design of economic, efficient, and robust catalysts for low-temperature RWGS reactions.


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About this article

Identifying the roles of Ce3+–OH and Ce–H in the reverse water–gas shift reaction over highly active Ni-doped CeO2 catalyst

Show Author's information Haidong Shen1, Yujuan Dong1, Shaowei Yang1, Yuan He1, Qimeng Wang1, Yueling Cao1, Wenbin Wang1, Tianshuai Wang1( ), Qiuyu Zhang1( ), Hepeng Zhang1,2( )
Xi’an Key Laboratory of Functional Organic Porous Materials, School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi’an 710129, China
Research & Development Institute of Northwestern Polytechnical University in Shenzhen, Shenzhen 518057, China

Abstract

Nickel-CeO2-based materials are commonly used for the thermal catalytic hydrogenation of CO2. However, high Ni loadings and low CO selectivity restrict their use in the reverse water–gas shift (RWGS) reaction. Herein, we demonstrate a highly active, robust, and low-Ni-doped (1.1 wt.%) CeO2 catalyst (1.0-Ni-CeO2). The Ni-based-mass-specific CO formation rate reaches up to 1,542 mmol·gNi−1·h−1 with 100% CO selectivity at 300 °C for 100 h, among the best values reported in the literature. Density functional theory (DFT) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) results reveal that the enhanced catalytic activity is attributed to the abundant Ce–H species, while the high selectivity results from low CO affinity. More importantly, a new reaction mechanism is proposed, which involves the reduction of bicarbonate to generate formate intermediate and CO by the H− released from Ce–H species. The new findings in this work will benefit the design of economic, efficient, and robust catalysts for low-temperature RWGS reactions.

Keywords: CO2 hydrogenation , Ni-doped CeO2, cerium hydride, mechanism investigation, reverse water–gas shift (RWGS) reaction

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Publication history
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Acknowledgements

Publication history

Received: 02 December 2021
Revised: 10 January 2022
Accepted: 30 January 2022
Published: 18 April 2022
Issue date: July 2022

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This work was financially supported by the Science and Technology Project of Shenzhen (No. JCYJ20190806155814624), the National Natural Science Foundation of China (No. 22002120) and the Fundamental Research Funds for the Central Universities (No. 3102017jc01001). We would like to thank the Analytical & Testing Center of Northwestern Polytechnical University for SEM, TEM, XRD, and XPS characterizations.

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