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A highly CO-tolerant atomically dispersed Pt catalyst for chemoselective hydrogenation

Nature Nanotechnology volume 14, pages 354–361 (2019)Cite this article

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Abstract

The hydrogenation activity of noble metal, especially platinum (Pt), catalysts can be easily inhibited by the presence of a trace amount of carbon monoxide (CO) in the reaction feeds. Developing CO-resistant hydrogenation catalysts with both high activity and selectivity is of great economic interest for industry as it allows the use of cheap crude hydrogen and avoids costly product separation. Here we show that atomically dispersed Pt over α-molybdenum carbide (α-MoC) constitutes a highly CO-resistant catalyst for the chemoselective hydrogenation of nitrobenzene derivatives. The Pt1/α-MoC catalyst shows promising activity in the presence of 5,000 ppm CO, and has a strong chemospecificity towards the hydrogenation of nitro groups. With the assistance of water, high hydrogenation activity can also be achieved using CO and water as a hydrogen source, without sacrificing selectivity and stability. The weakened CO binding over the electron-deficient Pt single atom and a new reaction pathway for nitro group hydrogenation confer high CO resistivity and chemoselectivity on the catalyst.

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Fig. 1: Structural characterization of the 0.25% Pt/α-MoC catalyst.
Fig. 2: The energy profiles for C6H5NO2 hydrogenation into C6H5NH2 on Pt1/α-MoC(111).
Fig. 3: The intrinsic hydrogenation TOF rate per Pt site for nitrobenzene over the 0.5% Pt/C and 0.25% Pt/α-MoC catalysts.

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Data Availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author, X.D.W., upon reasonable request.

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Acknowledgements

This work was financially supported by the Natural Science Foundation of China (21725301, 91645115, 21872104, 21473003, 51622211, 21473229 and 91545121) and the National Key R&D Program of China (2017YFB0602200). The electron microscopy work performed in the CAS Key Laboratory of Vacuum Sciences was supported in part by the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences (CAS) and the Pioneer Hundred Talents Program of the CAS. The XAFS experiments were conducted at the Shanghai Synchrotron Radiation Facility. The authors also acknowledge the innovation foundation of the Institute of Coal Chemistry, CAS, the Hundred-Talent Program of the CAS, the Shanxi Hundred-Talent Program and the National Thousand Young Talents Program of China. The scholarship under the International Postdoctoral Exchange Fellowship Program 2017 by the Office of China Postdoctoral Council (document 496 number: no. 32 Document of OCPC, 2017) is also gratefully acknowledged. The authors also appreciate B. Qiao for discussions and for providing the Pt1/FeOx single atom catalyst as a reference.

Author information

Author notes

  1. These authors contributed equally: Lili Lin, Siyu Yao, Rui Gao.

Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, College of Engineering and BIC-ESAT, Peking University, Beijing, China

    Lili Lin, Siyu Yao, Xuan Liang, Qiaolin Yu, Yuchen Deng, Mi Peng, Siwei Li & Ding Ma

  2. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, China

    Rui Gao, Jinjia Liu, Yong-Wang Li & Xiao-Dong Wen

  3. National Energy Centre for Coal to Liquids, Synfuels China Co. Ltd, Beijing, China

    Rui Gao, Jinjia Liu, Yong-Wang Li & Xiao-Dong Wen

  4. School of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot, China

    Rui Gao

  5. Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, China

    Zheng Jiang

  6. Beijing Advanced Innovation Center for Materials Genome Engineering, Industry–University Cooperation Base between Beijing Information S&TUniversity and Synfuels China Co. Ltd, Beijing, China

    Xiao-Dong Wen

  7. School of Physical Sciences and CAS Centre for Excellence in Topological Quantum Computation, University of Chinese Academy of Sciences, Beijing, China

    Wu Zhou

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Contributions

D.M. designed the research. L.L. performed most of the reactions. W.Z. performed the electron microscopy analyses. S.Y. and Z.J. carried out the X-ray structure characterization and analyses. R.G., Y.-W.L. and X.-D.W. completed the theoretical calculations. L.L., S.Y., W.Z. and D.M. wrote the paper. Other authors performed some of the experiments and revised the paper. All authors discussed the data and commented on the manuscript.

Corresponding authors

Correspondence to Wu Zhou or Ding Ma.

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The authors declare no competing interests.

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Journal peer review information: Nature Nanotechnology thanks Nigel Powell, Yung-Eun Sung and other anonymous reviewer(s) for their contribution to the peer review of this work.

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Lin, L., Yao, S., Gao, R. et al. A highly CO-tolerant atomically dispersed Pt catalyst for chemoselective hydrogenation. Nat. Nanotechnol. 14, 354–361 (2019). https://doi.org/10.1038/s41565-019-0366-5

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