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DFT calculation analysis of oxygen reduction activity and stability of bimetallic catalysts with Pt-segregated surface

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  • Special Issue Heterogeneous Catalysis Theory
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Abstract

The stability and oxygen reduction reaction (ORR) activity of the Pt-segregated surface in various Pt-M alloys (M: transition metals) are investigated through systematic DFT calculations on the thermodynamic (alloy formation energy and Pt surface segregation energy), surface chemical property (oxygen binding energy) and electronic (d-band center) properties. Factors affecting these properties, such as the atomic radii and surface energy of M and the electronic ligand interaction between Pt and M are analyzed as a function of outmost d electron numbers of M. It is shown that the electronic ligand interaction plays determining role in the alloy formation energy of various Pt-M alloys; the formation of Pt-segregated surface in Pt-M alloys is favored when alloying metals have higher surface energy and smaller radii than Pt; the oxygen binding energy on the Pt-segregated surface in Pt-M alloys varies approximately linearly with the d-band center of surface Pt atoms; the lattice strain and electronic ligand effects are simply additive in Pt-M alloys; the stain effect in Pt-M alloys nearly linearly affects the d-band center of the Pt-segregated surface in Pt-M alloys; transition metals with less than 10 d electrons mostly exhibit electron ligand effects which result in downshift of the d-band center of the segregated surface Pt atoms, while those with ten d electrons exhibit electron ligand effect upshifting the d-band center of the segregated Pt atoms.

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Authors and Affiliations

  1. College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430072, China

    Lihui Ou & Shengli Chen

  2. College of Chemistry and Chemical Engineering, Hunan University of Arts and Science, Changde, 415000, China

    Lihui Ou

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  1. Lihui Ou
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  2. Shengli Chen
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Correspondence to Shengli Chen.

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Ou, L., Chen, S. DFT calculation analysis of oxygen reduction activity and stability of bimetallic catalysts with Pt-segregated surface. Sci. China Chem. 58, 586–592 (2015). https://doi.org/10.1007/s11426-015-5324-y

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  • DOI: https://doi.org/10.1007/s11426-015-5324-y

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