Specific adsorption of halide and pseudohalide ions at electrochemically roughened versus smooth silver-aqueous interfaces

Joseph T Hupp, D. Larkin, Michael J. Weaver

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Abstract

The differential capacitance of electrochemically roughened silver surfaces in mixed perchlorate electrolytes containing chloride, bromide, iodide, thiocyanate, or azide anions has been measured as a function of electrode potential and anion concentration. These results are compared with corresponding data for electropolished silver in order to ascertain the influence of surface roughening on the double-layer structure and composition of polycrystalline silver-aqueous interfaces. The surface concentrations of specifically adsorbed anions were obtained from these capacitance-potential data using a "Hurwitz-Parsons" type of analysis. Although electrochemical roughening by means of a conventional oxidation-reduction cycle in chloride media is a prerequisite to the appearance of Surface-Enhanced Raman Scattering (SERS) for these adsorbates, it yields only moderate (ca. 1.5- to 2-fold) increases in the actual surface area and has a relatively minor effect on their average surface concentration. However, roughening does induce noticeable changes in the morphology of the capacitance-potential curves which are traced to alterations in the surface-crystallite structure. Comparisons between the potential dependence of SERS with corresponding capacitance-potential data indicate that anion coverages close to a monolayer are necessary for stable SERS. This is attributed to the stabilization of Raman-active silver clusters by surrounding adsorbed anions.

Original languageEnglish
Pages (from-to)429-451
Number of pages23
JournalSurface Science
Volume125
Issue number2
DOIs
Publication statusPublished - Feb 2 1983

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Condensed Matter Physics
  • Surfaces and Interfaces

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