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Mechanistic Insights into the Hydrogen Oxidation Reaction on PtNi Alloys in Alkaline Media: A First-Principles Investigation

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    Energy, Environmental, and Catalysis Applications

    Mechanistic Insights into the Hydrogen Oxidation Reaction on PtNi Alloys in Alkaline Media: A First-Principles Investigation
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    • Lianming Zhao*
      Lianming Zhao
      School of Materials Science and Engineering, Institute of Advanced Materials, China University of Petroleum, Qingdao, Shandong 266580, People’s Republic of China
      *Email: [email protected]
      More by Lianming Zhao
      Orcidhttp://orcid.org/0000-0002-9304-260X
    • Haijun Liu
      Haijun Liu
      School of Materials Science and Engineering, Institute of Advanced Materials, China University of Petroleum, Qingdao, Shandong 266580, People’s Republic of China
      More by Haijun Liu
    • Yonghui Liu
      Yonghui Liu
      School of Materials Science and Engineering, Institute of Advanced Materials, China University of Petroleum, Qingdao, Shandong 266580, People’s Republic of China
      More by Yonghui Liu
    • Xiaonan Han
      Xiaonan Han
      School of Materials Science and Engineering, Institute of Advanced Materials, China University of Petroleum, Qingdao, Shandong 266580, People’s Republic of China
      More by Xiaonan Han
    • Jing Xu
      Jing Xu
      School of Materials Science and Engineering, Institute of Advanced Materials, China University of Petroleum, Qingdao, Shandong 266580, People’s Republic of China
      More by Jing Xu
    • Wei Xing
      Wei Xing
      School of Materials Science and Engineering, Institute of Advanced Materials, China University of Petroleum, Qingdao, Shandong 266580, People’s Republic of China
      More by Wei Xing
      Orcidhttp://orcid.org/0000-0003-4098-4860
    • Wenyue Guo*
      Wenyue Guo
      School of Materials Science and Engineering, Institute of Advanced Materials, China University of Petroleum, Qingdao, Shandong 266580, People’s Republic of China
      *Email: [email protected]
      More by Wenyue Guo
      Orcidhttp://orcid.org/0000-0002-7537-984X
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    ACS Applied Materials & Interfaces

    Cite this: ACS Appl. Mater. Interfaces 2020, 12, 36, 40248–40260
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    https://doi.org/10.1021/acsami.0c09005
    Published August 18, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    The promising alkaline anion exchange membrane fuel cell suffers from sluggish kinetics of the hydrogen oxidation reaction (HOR). However, the puzzling HOR mechanism hinders the further development of highly active catalysts in alkaline media. In this work, we conducted detailed first-principles calculations to acquire a deep understanding of the alkaline HOR mechanism on PtNi bulk alloys [Pt3Ni(111), Pt2Ni2(111), and PtNi3(111)] and its surface alloy [PtNisurf(111)]. The full free energy profiles suggest that the HOR on PtNi alloys proceeds via the Tafel–Volmer mechanism, that is, the direct decomposition of H2 into two adsorbed H, followed by its reaction with OH– in the electrolyte, as the rate-determining step, to form H2O. Therefore, the HOR activity of PtNi alloys is solely impacted by the adsorption of hydrogen, rather than hydroxyl species, though the oxophilicity is also enhanced by alloying Pt with Ni. Thermodynamically, a moderate H adsorption free energy, ΔGH* ≈ 0.414 eV, is calculated to be an optimal candidate for the HOR at pH = 13. Alloying Pt with Ni can elevate the d-band center (εd), push the value of ΔGH* closer to 0.414 eV, and thus lower the free energy barrier (Ea) of the rate-determining Volmer reaction, leading to the highest HOR activity of PtNi3(111) among all considered PtNi alloys. This situation is further confirmed by both the microkinetic model and the Tafel plot, where PtNi3(111) exhibits the highest reaction rate (r = 9.42 × 103 s–1 site–1) and the largest exchange current density (i0 = 1.42 mA cm–2) for HOR in alkaline media. This work provides a fundamental understanding of the HOR mechanism and theoretical guidance for rational design of electrocatalysts for HOR in alkaline media.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.0c09005.

    • Bulk lattice parameters, Hirshfeld charge, and oxidation potential for Pt, Ni, and PtNi alloys; structures, DED map, and spin density for def-Pt3Ni(111) and def-PtNi3(111); possible H2O, OH, H2, and single/double H-adsorbed and co-adsorbed configurations and adsorption energy; relationship of H adsorption energy with the d-band center; DED map and spin density for the single H-adsorbed alloy surfaces; activation energy, equilibrium constant, and rate constant of the elementary HORs; phase diagram and free energy diagram of the Tafel–Volmer mechanism for Pt(111) and Ni(111); free energy diagram of the Tafel–Volmer mechanism for def-Pt3Ni(111) and def-PtNi3(111); and activation energy curve as functions of charge and electrode potential on Pt(111) (PDF)

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    Cite this: ACS Appl. Mater. Interfaces 2020, 12, 36, 40248–40260
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsami.0c09005
    Published August 18, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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