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Angewandte Chemie International Edition· 2017Q1

Co‐adsorption of Cations as the Cause of the Apparent pH Dependence of Hydrogen Adsorption on a Stepped Platinum Single‐Crystal Electrode

Xiaoting Chen, Ian T. McCrum, Kathleen Schwarz, Michael J. Janik et al.

Short summary

Co-adsorbed alkali metal cations weaken hydroxyl adsorption at step sites on Pt(553) electrodes, causing an apparent pH dependence of hydrogen adsorption.

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Key points

  • Alkali metal cations (Li+, Na+, K+, Cs+) influence the pH-dependent voltammetric peak of Pt(553) electrodes.
  • Co-adsorbed cations weaken hydroxyl (*OH) adsorption at step sites.
  • This weakening causes a positive shift in the potential of step-related peaks.
  • Density functional calculations confirm cation-hydroxyl co-adsorption as the cause of apparent pH dependence for hydrogen adsorption at platinum step sites.

AI-generated from the title and abstract; the full text is not read.

Abstract

Abstract The successful deployment of advanced energy‐conversion systems depends critically on our understanding of the fundamental interactions of the key adsorbed intermediates (hydrogen *H and hydroxyl *OH) at electrified metal–aqueous electrolyte interfaces. The effect of alkali metal cations (Li + , Na + , K + , Cs + ) on the non‐Nernstian pH shift of the step‐related voltammetric peak of the Pt(553) electrode is investigated over a wide pH window (1 to 13) by means of experimental and computational methods. The co‐adsorbed alkali cations along the step weaken the OH adsorption at the step sites, causing a positive shift of the potential of the step‐related peak on Pt(553). Density functional calculations explain the observations on the identity and concentration of alkali cations on the non‐Nernstian pH shift, and demonstrate that cation–hydroxyl co‐adsorption causes the apparent pH dependence of “hydrogen” adsorption in the step sites of platinum electrodes.

The authors' abstract, as published at the source. Angewandte Chemie International Edition, 2017 · DOI ↗

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