The adsorption of lead on clean and sulfur-modified
nickel surfaces was studied as a function of immersion
time. The effect of preadsorbed sulfur and lead adsorption on
nickel oxidation was also examined by
open-circuit potential (OCP) measurements. Sulfur adsorbed on
nickel inhibits the formation of the inner
NiO layer, which results in an enhanced nickel oxidation/dissolution in
aqueous solutions. The adsorption
of lead is enhanced by as much as 1200% when the nickel electrode is
first modified by a monolayer of
adsorbed sulfur. The chemical shift in Pb(4f) binding
energies indicates that lead (Pb2+) ions
interact
directly with the preadsorbed sulfur on nickel. Lead adsorbed on
sulfur-modified nickel electrode is also
found to retard the oxidation/dissolution of nickel, which is enhanced
by sulfur. On sulfur-modified nickel
surfaces, 70% of the lead adsorption occurs during the initial 30 s of
immersion. The rate of lead adsorption
approaches zero after an immersion time of 10 min. On the basis of
the observations of this study, a model
for the sulfur-induced lead adsorption has been
formulated.
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