| Autor: |
Liu J; Leiden Institute of Chemistry, Leiden University, Leiden 2333 CC, The Netherlands., Hagopian A; Leiden Institute of Chemistry, Leiden University, Leiden 2333 CC, The Netherlands., McCrum IT; Department of Chemical and Biomolecular Engineering, Clarkson University, Potsdam, New York 13699, United States., Doblhoff-Dier K; Leiden Institute of Chemistry, Leiden University, Leiden 2333 CC, The Netherlands., Koper MTM; Leiden Institute of Chemistry, Leiden University, Leiden 2333 CC, The Netherlands. |
| Jazyk: |
angličtina |
| Zdroj: |
The journal of physical chemistry. C, Nanomaterials and interfaces [J Phys Chem C Nanomater Interfaces] 2024 Aug 29; Vol. 128 (36), pp. 15019-15028. Date of Electronic Publication: 2024 Aug 29 (Print Publication: 2024). |
| DOI: |
10.1021/acs.jpcc.4c05193 |
| Abstrakt: |
Hydrogen adsorption on platinum (Pt) single-crystal electrodes has been studied intensively in both experiments and computations. Yet, the precise origin and nature of the repulsive interactions observed between hydrogen adsorbates (H ads ) have remained elusive. Here, we use first-principles density functional theory calculations to investigate in detail the interactions between H ads on Pt(111), Pt(100), and Pt(110) surfaces. The repulsive interaction between H ads on Pt(111) is deconvoluted into three different physical contributions, namely, (i) electrostatic interactions, (ii) surface distortion effect, and (iii) surface coordination effect. The long-range electrostatic interaction, which is generally considered the most important source of repulsive interactions in surface adsorption, was found to contribute less than 30% of the overall repulsive interaction. The remaining >70% arises from the other two contributions, underscoring the critical influence of surface-mediated interactions on the adsorption process. Surface distortion and coordination effects are found to strongly depend on the coverage and adsorption geometry: the effect of surface distortion dominates when adsorbates reside two or more Pt atoms apart; the effect of surface coordination dominates if hydrogen is adsorbed on neighboring adsorption sites. The above effects are considerably less pronounced on Pt(100) and Pt(110), therefore resulting in weaker interactions between H ads on these two surfaces. Overall, the study highlights the relevance of surface-mediated effects on adsorbate-adsorbate interactions, such as the often-overlooked surface distortion. The effect of these interactions on the hotly debated adsorption site for the adsorbed hydrogen intermediate in the hydrogen evolution reaction is also discussed.
Competing Interests: The authors declare no competing financial interest.
(© 2024 The Authors. Published by American Chemical Society.) |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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