Abstract
The adsorption of saccharin on roughened nickel electrode has been studied with cyclic voltammetry (CV) and surface-enhanced Raman spectroscopy as well as complementary discrete Fourier transform calculations. CV measurements reveal a strong influence of both chloride concentration and pH of electrolyte on nickel surface and the inhibitory effect on nickel oxidation by the saccharin addition. Surface-enhanced Raman spectroscopy (SERS) measurements provide evidence for the strong interaction between the Ni surface and saccharin additives and dependence on the electrode potential. The overall behavior observed in SERS is explained based on the normal Raman spectra of saccharinate anion and its nickel-saccharinate complexes. Above the potential of zero charge (pzc) of the Ni surface, saccharinate-associated SERS peaks are dominant with O-bound nickel-saccharinate characteristics. Below the pzc, the SERS profile experiences a huge intensity enhancement and spectral change as well as substantial Raman frequency shifts. These shifts are interpreted in terms of a saccharinate-Ni complex, with both O and N bonding to the Ni electrode surface.
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