Scanning electrochemical microscopy: Surface interrogation of adsorbed hydrogen and the open circuit catalytic decomposition of formic acid at platinum

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Abstract

The surface interrogation mode of scanning electrochemical microscopy (SECM) is extended to the in situ quantification of adsorbed hydrogen, H ads, at polycrystalline platinum. The methodology consists of the production, at an interrogator electrode, of an oxidized species that is able to react with Hads on the Pt surface and report the amounts of this adsorbate through the SECM feedback response. The technique is validated by comparison to the electrochemical underpotential deposition (UPD) of hydrogen on Pt. We include an evaluation of electrochemical mediators for their use as oxidizing reporters for adsorbed species at platinum; a notable finding is the ability of tetramethyl-p-phenylenediamine (TMPD) to oxidize (interrogate) H ads on Pt at low pH (0.5 M H2SO4 or 1 M HClO4) and with minimal background effects. As a case study, the decomposition of formic acid (HCOOH) in acidic media at open circuit on Pt was investigated. Our results suggest that formic acid decomposes at the surface of unbiased Pt through a dehydrogenation route to yield Hads at the Pt surface. The amount of Hads depended on the open circuit potential (OCP) of the Pt electrode at the time of interrogation; at a fixed concentration of HCOOH, a more negative OCP yielded larger amounts of Hads until reaching a coulomb limiting coverage close to 1 UPD monolayer of H ads. The introduction of oxygen into the cell shifted the OCP to more positive potentials and reduced the quantified Hads; furthermore, the system was shown to be chemically reversible, as several interrogations could be run consecutively and reproducibly regardless of the path taken to reach a given OCP.

Original languageEnglish (US)
Pages (from-to)5121-5129
Number of pages9
JournalJournal of the American Chemical Society
Volume132
Issue number14
DOIs
StatePublished - Apr 14 2010
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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