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A mechanistic study of CO removal on a small H-saturated platinum cluster

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Abstract

CO poisoning to platinum catalysts has long been recognized as one of the major technical obstacles in heterogeneous catalysis and its successful removal represents a significant challenge to a wide variety of applications. Using density functional theory (DFT), we performed systematic theoretical calculations to explore the CO removal mechanisms, in the presence of hydrogen, via oxidation by oxygen to form CO2 or reduction by hydrogen to form formaldehyde using a subnano Pt cluster as a model for catalyst nanoparticles. We show that CO oxidation is both thermochemically and kinetically difficult at low H coverage but becomes very exothermic with a moderate activation barrier at high H coverage, suggesting that the oxidation can be carried out readily at elevated temperatures. Doping the Pt cluster with Ru can significantly improve the oxidation thermochemical energy and moderately reduce the activation barrier. The results are consistent with experimental observations. We found that CO reduction by hydrogen to form formaldehyde is moderately endothermic. However, the reaction is predicted to be kinetically difficult due to the relatively high activation barriers associated with the sequential H attacks to the CO molecule.

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Authors and Affiliations

  1. Institute of Theoretical Chemistry and Computational Materials Science, China University of Geosciences, Wuhan, 430074, China

    ChengGang Zhou, ShuJuan Yao, Bo Han, JinPing Wu & HanSong Cheng

  2. Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, 315201, China

    Liang Chen

  3. Department of Physics, Pennsylvania State University, Berks Campus, Reading, PA, 19610, USA

    Robert C. Forrey

  4. Air Products and Chemicals, Inc., 7201 Hamilton Boulevard, Allentown, PA, 18195-1501, USA

    HanSong Cheng

Authors
  1. ChengGang Zhou
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  2. ShuJuan Yao
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  3. Bo Han
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  4. Liang Chen
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  5. JinPing Wu
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  6. Robert C. Forrey
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Correspondence to JinPing Wu or HanSong Cheng.

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Supported by the National Natural Science Foundation of China for Youth (Grant No. 20703040)

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Zhou, C., Yao, S., Han, B. et al. A mechanistic study of CO removal on a small H-saturated platinum cluster. Sci. China Ser. B-Chem. 51, 1187–1196 (2008). https://doi.org/10.1007/s11426-008-0135-z

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  • DOI: https://doi.org/10.1007/s11426-008-0135-z

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