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Journal of Applied Electrochemistry

, Volume 38, Issue 7, pp 897–906 | Cite as

SFG and DFG investigation of Au(111), Au(210), polycrystalline Au, Au–Cu and Au–Ag–Cu electrodes in contact with aqueous solutions containing KCN and 4-cyanopyridine

  • Benedetto Bozzini
  • Bertrand Busson
  • Claudio MeleEmail author
  • Abderrahmane Tadjeddine
Original Paper

Abstract

We report on potential-dependent in situ SFG and DFG spectroscopy carried out at Au(111), Au(210), polycrystalline Au, Au–Cu and Au–Ag–Cu electrodes in contact with aqueous solutions containing CN and 4-cyanopyridine (4CP). Spectroelectrochemical work was complemented by cyclic voltammetry. The chief stress has been placed on systematising and quantifying the interaction between 4CP and CN and the attending effects on the vibrational and electronic structures of the interface. The voltammetric behaviour of the investigated electrodes, modified by the addition of 4CP to the CN electrolyte, denote changes in the CN adsorption characteristics and effects of the adsorbed CN layer on the electrodic reactivity of 4CP. The differences among the investigated electrodes can be explained in terms of their respective degrees of atomic packing or with alloying effects on the stability of adsorbed CN. The potential-dependent spectra have been analysed quantitatively with a model for the second order non linear susceptibility accounting for vibrational and electronic effects. The spectral changes induced by addition of 4CP denote interaction of the aromatic with the electrode through the CN monolayer. The non-resonant contribution yields information on the effects of 4CP on the fine structure of the bound electron density of states.

Keywords

SFG DFG Cyanide 4-cyanopyridine Au(111) Au(210) Au–Cu Au–Ag–Cu 

Notes

Acknowledgements

Highly qualified and continuous technical assistance by the SFG collaborators and CLIO staff, Bâtiment 209D, Centre Universitaire Paris Sud, 91405 Orsay, France, is gratefully acknowledged.

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Copyright information

© Springer Science+Business Media B.V. 2008

Authors and Affiliations

  • Benedetto Bozzini
    • 1
  • Bertrand Busson
    • 2
  • Claudio Mele
    • 1
    Email author
  • Abderrahmane Tadjeddine
    • 3
  1. 1.Dipartimento di Ingegneria dell’InnovazioneUniversità di LecceLecceItaly
  2. 2.CLIO-LCP, Université Paris-SudOrsay CedexFrance
  3. 3.UDIL-CNRS, Bat. 201, centre Universitaire Paris-SudOrsay CedexFrance

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