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

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.

SUBMITTER: Chen X 

PROVIDER: S-EPMC5991472 | biostudies-literature | 2017 Nov

REPOSITORIES: biostudies-literature

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

Chen Xiaoting X   McCrum Ian T IT   Schwarz Kathleen A KA   Janik Michael J MJ   Koper Marc T M MTM  

Angewandte Chemie (International ed. in English) 20171023 47

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<sup>+</sup> , Na<sup>+</sup> , K<sup>+</sup> , Cs<sup>+</sup> ) 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  ...[more]

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