Nm. Markovic et al., OXYGEN REDUCTION ON PLATINUM LOW-INDEX SINGLE-CRYSTAL SURFACES IN ALKALINE-SOLUTION - ROTATING-RING DISK(PT(HKL)) STUDIES, Journal of physical chemistry, 100(16), 1996, pp. 6715-6721
The first results of a study of the oxygen reduction reaction on a rot
ating ring-disk electrode using single-crystal Pt disk electrodes in a
lkaline solution are presented. The order of activity of Pt(hkl) in 0.
1M KOH increased in the sequence (100) < (110) < (111) for both oxygen
and peroxide reduction. These differences are attributed to the struc
ture sensitivity of hydroxyl anion (OH.) adsorption on Pt(hkl) and its
inhibiting (site blocking) effect on oxygen kinetics. Two different t
ypes of OHads occur on Pt(100) and Pt(110), a reversible OHIV, and an
irreversible OHir, while only the reversible form is formed on Pt(111)
. Very small fluxes (I-R/N << 0.011(D)) of peroxide were detected at t
he ring at potentials where the surfaces have only the reversible form
of OHads. More peroxide (I-R/N < 0.03I(D)) was found with the Pt(100)
and Pt(110)surfaces in the potential region where irreversible adsorp
tion occurs. The mechanism of O-2 reduction was also affected by adsor
bed hydrogen with increased formation of peroxide ions in this potenti
al region; correspondingly, adsorbed hydrogen was found to have an inh
ibiting effect on peroxide reduction, the effect decreasing in the ord
er (111) > (100) >> (110).