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Research Article

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

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
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Graphical Abstract

The successful doping of Ni atoms into the CeO2 structure remarkably enhances the reverse water–gas shift (RWGS) reaction activities owing to the high H2 heterolytic dissociation capacity and stable Ce–H species.

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 CeO2reverse water–gas shift (RWGS) reactioncerium hydridemechanism investigation

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Nano Research
Volume 15 Issue 7,
July 2022
Pages 5831-5841
DOI: 10.1007/s12274-022-4207-8
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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Received: 02 December 2021
Revised: 10 January 2022
Accepted: 30 January 2022
Published: 18 April 2022
© Tsinghua University Press 2022
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