Single-atom catalysis of CO oxidation using Pt1/FeOx

Abstract

Platinum-based heterogeneous catalysts are critical to many important commercial chemical processes, but their efficiency is extremely low on a per metal atom basis, because only the surface active-site atoms are used. Catalysts with single-atom dispersions are thus highly desirable to maximize atom efficiency, but making them is challenging. Here we report the synthesis of a single-atom catalyst that consists of only isolated single Pt atoms anchored to the surfaces of iron oxide nanocrystallites. This single-atom catalyst has extremely high atom efficiency and shows excellent stability and high activity for both CO oxidation and preferential oxidation of CO in H2. Density functional theory calculations show that the high catalytic activity correlates with the partially vacant 5d orbitals of the positively charged, high-valent Pt atoms, which help to reduce both the CO adsorption energy and the activation barriers for CO oxidation.

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Figure 1: HAADF-STEM images of samples A and B.
Figure 2: X-ray absorption studies.
Figure 3: In situ FTIR spectra of CO adsorption for samples A and B.
Figure 4: The proposed reaction pathways for CO oxidation on the Pt1/FeOx catalyst (sample A).

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Acknowledgements

We thank Y. Huang, S. Zhang, T. Hu, J. Zhang, Y. Xie and L. Zheng for their help in the EXAFS measurements and data analysis, and L. Li for infrared measurements and discussion. We also acknowledge E. Okunishi for assistance on operating the JEM ARM-200F TEM/STEM. Particularly, we thank Jeffrey T. Miller for his suggestions and comments on EXAFS analysis during the manuscript revision process. Financial support for this research work from the National Science Foundation of China (20325620, 20773124) and the Ministry of Science and Technology of China (NKBRSF 2007CB815200, 2011CB932400) is also acknowledged. Part of the electron microscopy work was conducted at the Oak Ridge National Laboratory's High Temperature Materials Laboratory, sponsored by the US Department of Energy, Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Program. The calculations were performed at the Shanghai Supercomputing Center and the Computer Network Information Center, Chinese Academy of Sciences.

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B. Qiao performed the catalyst preparation, characterizations and catalytic tests. X. Yang and J. Li conducted DFT calculations and wrote part of the paper (calculation). L.F. Allard and J. Liu conducted the STEM examinations and contributed to writing the STEM sections. Z. Jiang and Y. Cui performed measurements and data analyses of EXAFS. A. Wang and T. Zhang designed the study, analysed the data and co-wrote the paper. All the authors discussed the results and commented on the manuscript.

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Correspondence to Jingyue Liu or Jun Li or Tao Zhang.

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Qiao, B., Wang, A., Yang, X. et al. Single-atom catalysis of CO oxidation using Pt1/FeOx. Nature Chem 3, 634–641 (2011). https://doi.org/10.1038/nchem.1095

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