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Electrocapillary coupling during electrosorption.

Qibo Deng1, Jörg Weissmüller

  • 1Institut für Werkstoffphysik und Werkstofftechnologie, Technische Universität Hamburg-Harburg , Hamburg, 21073 Germany.

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The electrocapillary coupling coefficient (ς) reveals surface details missed by cyclic voltammetry. Its behavior during electrosorption on Au, Pt, and Pd provides new insights into electrode surface processes.

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Area of Science:

  • Electrochemistry
  • Surface Science
  • Materials Science

Background:

  • The electrocapillary coupling coefficient (ς) quantifies electrode potential response to surface strain.
  • Understanding ς(E) is crucial for characterizing electrode-surface interactions.
  • Simultaneous analysis with cyclic voltammetry (CV) offers deeper insights.

Purpose of the Study:

  • To investigate the electrocapillary coupling coefficient (ς) across extended potential intervals on Au, Pt, and Pd electrodes.
  • To correlate ς(E) behavior with electrosorption of oxygen and hydrogen species.
  • To identify details in ς(E) graphs that are not apparent in CVs.

Main Methods:

  • Dynamic electro-chemo-mechanical analysis.
  • Simultaneous measurement of ς(E) and cyclic voltammetry.
  • Study on gold, platinum, and palladium surfaces.

Main Results:

  • The magnitude and sign of ς varied significantly during potential scans.
  • Capacitive processes on clean surfaces showed ς < 0.
  • Oxygen-covered surfaces exhibited different ς signs on Au (ς < 0) versus Pt/Pd (ς > 0).
  • Hydrogen electrosorption generally showed ς > 0, consistent with tensile strain enhancing binding.
  • Significant hysteresis in oxygen electrosorption was observed, questioning its measurement via strain-induced potential response.

Conclusions:

  • The electrocapillary coupling coefficient (ς) provides complementary information to CV, highlighting subtle surface phenomena.
  • Surface strain effects differ between clean and adsorbate-covered electrodes.
  • The observed hysteresis in oxygen electrosorption warrants further investigation regarding measurement techniques.