Solvent effects in metal underpotential deposition on single crystal metal surfaces

Xuekun Xing, In Tae Bae, Daniel Alberto Scherson

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

The underpotential deposition (upd) of Pb and Cd on Ag(111) and Au(111) single crystals grown on freshly cleaved mica has been examined in propylene carbonate (PC), water, tetrahydrofuran (THF), and dimethoxyethane (DME) by cyclic voltammetric techniques. Insight into the cleanliness of the single crystal metal electrode/non-aqueous electrolyte interfaces was gained from a comparison of the potential (E) dependence of the differential capacity (C) in PC solutions with that reported in aqueous media. The cyclic voltammetric features for the Pb Ag(111) and Pb Au(111) upd systems in PC were found to be very similar to those obtained in aqueous media. This behavior was unlike that observed for the upd of Cd on these single crystal substrates in the same two solvents, for which the differences in the voltammetric features, especially in the case of Ag(111), were quite substantial. This latter effect has been ascribed, in part, to the ability of Cd ad-ions to undergo partial discharge on the electrode surface, a factor that changes the solvation characteristics of the adsorbed species and thus modifies the energetics and kinetics of the upd process. For solvents of low dielectric constant, ie THF and DME, the same four upd/substrate systems yielded highly distorted cyclic voltammetry curves. This has been tentatively attributed to extensive ion pairing both at the interface and in the bulk electrolyte. The presence of ion-pairs in the solution phase was evidenced by the lifting of the degeneracy of the v4 mode of the perchlorate ion (as monitored by transmission FTIR measurements), for which the detailed nature of the band splitting was found to be metal-ion specific.

Original languageEnglish
Pages (from-to)29-36
Number of pages8
JournalElectrochimica Acta
Volume40
Issue number1
DOIs
Publication statusPublished - 1995 Jan 1
Externally publishedYes

Fingerprint

Metals
Single crystals
Propylene
Carbonates
Ions
Electrolytes
Electrodes
Partial discharges
Solvation
Mica
Substrates
Cyclic voltammetry
Metal ions
Permittivity
Kinetics
Water
propylene carbonate
1,2-dimethoxyethane
tetrahydrofuran

Keywords

  • double layer capacity
  • ion pair
  • single crystal
  • solvent effects
  • upd

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Electrochemistry

Cite this

Solvent effects in metal underpotential deposition on single crystal metal surfaces. / Xing, Xuekun; Bae, In Tae; Scherson, Daniel Alberto.

In: Electrochimica Acta, Vol. 40, No. 1, 01.01.1995, p. 29-36.

Research output: Contribution to journalArticle

Xing, Xuekun ; Bae, In Tae ; Scherson, Daniel Alberto. / Solvent effects in metal underpotential deposition on single crystal metal surfaces. In: Electrochimica Acta. 1995 ; Vol. 40, No. 1. pp. 29-36.
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