Efficient gold and silver electrodes for surface enchanced raman spectral studies of electrochemical systems: The behaviour of pyridine and naphthalene adsorbed on roughened gold electrodes

A method is described whereby surface enhanced Raman (SER) active electrode surfaces of gold and silver may be made without recourse to the oxidation—reduction techniques which have been used hitherto. This method involves electroplating at low current density from dilute (< 10−2M) solutions of a suitable salt or complex in the absence of supporting electrolyte. Scanning electron microscopy shows the surfaces to consist of small spherical particles of fairly constant diameter packed together on the electrode. The sphere diameters are typically 70 nm (gold) and 180 nm (silver) for electrodes prepared in this manner. These electrodes exhibit intense SER scattering and have advantages over oxidation—reduction roughened electrodes. As examples of their utility some results are presented relating to the gold/pyridine and gold/naphthalene systems and these are discussed in relation to results obtained by other workers in similar systems using different methods, i.e., ellipsometry and differential capacitance variation.

[1]  B. Pettinger,et al.  Surface plasmon enhanced Raman scattering frequency and angular resonance of Raman scattered light from pyridine on Au, Ag and Cu electrodes , 1980 .

[2]  C. Kunz,et al.  Optical constants from the far infrared to the x-ray region: Mg, Al, Cu, Ag, Au, Bi, C, and Al 2 O 3 , 1975 .

[3]  I. Pockrand.  Raman spectroscopy of pyridine-exposed Ag, Cu and Au films in UHV. A comparative study , 1982 .

[4]  Martin Moskovits,et al.  Surface roughness and the enhanced intensity of Raman scattering by molecules adsorbed on metals , 1978 .

[5]  M. Fleischmann,et al.  Raman spectroscopic investigation of silver electrodes , 1975 .

[6]  John O’M. Bockris,et al.  Adsorption of anions at the solid-solution interface. Ellipsometric study , 1970 .

[7]  D. L. Jeanmaire,et al.  Surface raman spectroelectrochemistry: Part I. Heterocyclic, aromatic, and aliphatic amines adsorbed on the anodized silver electrode , 1977 .

[8]  M. Albrecht,et al.  The physical and chemical characterization of electrochemically reformed silver surfaces , 1980 .

[9]  J. Creighton,et al.  Factors influencing the enhancement of raman spectral intensity from a roughened silver surface: The adsorption and surface Raman scattering of 2-amino 5-nitro pyridine , 1982 .

[10]  Mino Green,et al.  The Adsorption of Aromatic Hydrocarbons at the Gold Electrolyte Interface , 1963 .

[11]  R. Waser,et al.  An electrochemical study of the adsorption of pyridine and chloride ions on smooth and roughened silver surfaces , 1981 .

[12]  B. Pettinger,et al.  Anguler-resolved raman spectroscopy of pyridine on copper and gold electrodes , 1980 .

[13]  M. Kerker,et al.  Surface enhanced Raman scattering (SERS) of citrate ion adsorbed on colloidal silver. , 1980, Applied optics.

[14]  M. Breiter.  Comparative voltammetric study of methanol oxidation and adsorption on noble metal electrodes in perchloric acid solutions , 1963 .