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Double Layer at the Pt(111)-Aqueous Electrolyte Interface: Potential of Zero Charge and Anomalous Gouy-Chapman Screening.

Kasinath OjhaNakkiran ArulmozhiDiana AranzalesMarc T M Koper
Published in: Angewandte Chemie (International ed. in English) (2019)
We report, for the first time, the observation of a Gouy-Chapman capacitance minimum at the potential of zero charge of the Pt(111)-aqueous perchlorate electrolyte interface. The potential of zero charge of 0.3 V vs. NHE agrees very well with earlier values obtained by different methods. The observation of the potential of zero charge of this interface requires a specific pH (pH 4) and anomalously low electrolyte concentrations (<10-3  m). By comparison to gold and mercury double-layer data, we conclude that the diffuse double layer structure at the Pt(111)-electrolyte interface deviates significantly from the Gouy-Chapman theory in the sense that the electrostatic screening is much better than predicted by purely electrostatic mean-field Poisson-Boltzmann theory.
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