Surface platinum hydride structures may exist and play a potentially important role during electrocatalysis and cathodic corrosion of Pt(111). Earlier work on platinum hydrides suggests that Pt may form clusters with multiple equivalents of hydrogen. Here, using thermodynamic methods and density functional theory, we compared several surface hydride structures on Pt(111). The structures contain multiple monolayers of hydrogen in or near the surface Pt layer. The hydrogen in these structures may bind the subsurface or reconstruct the surface both in the set of initial configurations and in the resulting (meta)stable structures. Multilayer stable configurations share one monolayer of subsurface H stacking between the top two Pt layers. The structure containing two monolayers (MLs) of H is formed at −0.29 V vs normal hydrogen electrode, is locally stable with respect to configurations with similar H densities, and binds H neutrally. Structures with 3 and 4 ML H form at −0.36 and −0.44 V, respectively, which correspond reasonably well to the experimental onset potential of cathodic corrosion on Pt(111). For the 3 ML configuration, the top Pt layer is reconstructed by interstitial H atoms to form a well-ordered structure with Pt atoms surrounded by four, five, or six H atoms in roughly square-planar and octahedral coordination patterns. Our work provides insight into the operando surface state during low-potential reduction reactions on Pt(111) and shows a plausible precursor for cathodic corrosion.
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7 January 2023
Research Article|
January 04 2023
Computational description of surface hydride phases on Pt(111) electrodes
Special Collection:
Chemical Physics of Electrochemical Energy Materials
Selwyn Hanselman
;
Selwyn Hanselman
(Conceptualization, Data curation, Formal analysis, Investigation, Methodology, Writing – original draft, Writing – review & editing)
1
Leiden Institute of Chemistry, Leiden University
, P.O. Box 9502, Leiden 2300 RA, The Netherlands
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Federico Calle-Vallejo
;
Federico Calle-Vallejo
(Supervision, Writing – review & editing)
2
Nano-Bio Spectroscopy Group and European Theoretical Spectroscopy Facility (ETSF), Department of Polymers and Advanced Materials: Physics, Chemistry and Technology, University of the Basque Country UPV/EHU
, Av. Tolosa 72, 20018 San Sebastián, Spain
3
IKERBASQUE, Basque Foundation for Science
, Plaza de Euskadi 5, 48009 Bilbao, Spain
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Marc T. M. Koper
Marc T. M. Koper
a)
(Conceptualization, Funding acquisition, Supervision, Writing – review & editing)
1
Leiden Institute of Chemistry, Leiden University
, P.O. Box 9502, Leiden 2300 RA, The Netherlands
a)Author to whom correspondence should be addressed: m.koper@chem.leidenuniv.nl
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a)Author to whom correspondence should be addressed: m.koper@chem.leidenuniv.nl
Note: This paper is part of the JCP Special Topic on Chemical Physics of Electrochemical Energy Materials.
J. Chem. Phys. 158, 014703 (2023)
Article history
Received:
September 12 2022
Accepted:
December 07 2022
Citation
Selwyn Hanselman, Federico Calle-Vallejo, Marc T. M. Koper; Computational description of surface hydride phases on Pt(111) electrodes. J. Chem. Phys. 7 January 2023; 158 (1): 014703. https://doi.org/10.1063/5.0125436
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