THE ELECTROCHEMICAL STABILITY OF MODEL INHIBITORS - A DEMS STUDY ON ADSORBED BENZENE, ANILINE AND PYRIDINE ON MONOCRYSTALLINE AND POLYCRYSTALLINE PT, RH AND PD ELECTRODES
U. Schmiemann et al., THE ELECTROCHEMICAL STABILITY OF MODEL INHIBITORS - A DEMS STUDY ON ADSORBED BENZENE, ANILINE AND PYRIDINE ON MONOCRYSTALLINE AND POLYCRYSTALLINE PT, RH AND PD ELECTRODES, Electrochimica acta, 39(4), 1994, pp. 561-576
The different metals show remarkable differences concerning the stabil
ity of the adsorbed layers. On Pt, benzene is Completely oxidized to C
O2 at potentials where oxygen adsorbes, whereas on Rh and Pd a part of
the adsorbed benzene starts being desorbed without oxidation at poten
tials where the oxide layer is formed. A negative going sweep after ad
sorption leads to formation of benzene and/or cyclohexane. From Pt and
Pd, cathodic desorption is nearly complete, whereas from Rh only 15%
of the adsorbate is cathodically desorbable. The anodic desorption pro
ducts of preadsorbed aniline are CO2 (on Pd) or CO2, HCN and NO (on Pt
and Rh). A quantitative evaluation shows that the largest part of the
total adsorbed nitrogen yields NO3-, being the final product of a rea
ction sequence with HCN and NO as intermediates. Oxidation of pyridine
on Pt leads to formation of CO2 and, at higher potentials, HCN and NO
. Oxidation therefore starts at the carbon atoms. Surface concentratio
ns indicate eta6-adsorption for aniline and benzene on Pt and Pd and p
yridine on Pt. On Rh, the maximum coverages are less than one monolaye
r, probably due to strong competitive adsorption of sulfate.