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Mechanism of CO preferential oxidation catalyzed by Cu n Pt (n = 3–12): a DFT study

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Abstract

The CO preferential oxidation reaction (PROX) is particularly well suited for hydrogen purification for proton exchange membrane fuel cell applications. In this work, the mechanism of CO-PROX catalyzed by Cu n Pt (n = 3–12) clusters has been studied by density functional theory calculations. The calculated results indicate that the most favored adsorption site of H2 for all clusters is on the Pt sites, and O2 prefers to bind on Cu sites and CO bind on Pt sites. The lowest energy barrier for hydrogen dissociation is 0.02 eV. Smaller H–Pt bond length of Cu n PtH2 corresponds to larger H–H bond length. CO-PROX occurs via the main intermediates of COOH and OH. Cu6Pt is proposed as the most effective catalyst for CO-PROX. To understand the high catalytic activity of Cu n Pt clusters, the nature of the interaction between adsorbate and substrate is also analyzed by detailed electronic local density of states. These findings enrich applications of Cu-based materials to the field of high-activity catalysts.

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (grant no. 20603021), the Natural Science Foundation of Shanxi (grant no. 2013011009-6), the High School 131 Leading Talent Project of Shanxi, Undergraduate Training Programs for Innovation and Entrepreneurship of Shanxi Province (grant nos. 105088, 2015537) and Shanxi Normal University (SD2013CXCY-65), and Teaching Reform Project of Shanxi Normal University (SD2013JGXM-51).

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Authors and Affiliations

  1. School of Chemistry and Material Science, Shanxi Normal University, Linfen, 041004, China

    Xiaona Dong, Caixia Wen, Ningning Ren, Zhaoru Cao & Naying Liu

  2. Department of Endocrinology, Beijing Electric Power Hospital, Beijing, 10073, China

    Ling Ling Guo

  3. School of Chemistry and Material Science, School of Modern Arts and Sciences, Shanxi Normal University, Linfen, 041004, China

    Ling Guo

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  1. Xiaona Dong
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Correspondence to Ling Guo.

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Dong, X., Guo, L., Wen, C. et al. Mechanism of CO preferential oxidation catalyzed by Cu n Pt (n = 3–12): a DFT study. Res Chem Intermed 41, 10049–10066 (2015). https://doi.org/10.1007/s11164-015-2012-7

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