We have found an excellent CO tolerance at Pt anodes alloyed with the secon
d metals in spite of the formation of Pt skin layer (ca. 1-2 nm in thicknes
s) over the alloy surfaces due to the dissolution of the second metals and
proposed a new mechanism for the catalysis. In this study, ATR-SEIRAS, coup
led with CV measurement, was used to observe the oxidation process of adsor
bed CO on the typical Pt-Fe alloy. The ahoy anode exhibits a lower saturate
d coverage with CO than that of pure Pt Linear CO is observed predominantly
on the alloy electrode, differing from both of linear and bridged CO besid
es COOH on the pure Pt The negative-shift of the wavenumber for the linear
CO stretching and the broadening of the half-wave width at the ahoy also in
dicate the weakening of metal-CO banding and the increased mobility of the
adsorbed CO, respectively. As a presumable effect of the electronic structu
re change at the Pt skin, the dissociation/oxidation of adsorbed water as w
ell. as a formation of adsorbed HOOH species are clearly observed beyond 0.
6 V in the electrolyte solution without CO. The mechanism of CO tolerance a
t the Pt skin on top of the alloy surface with an increased d-band vacancy,
proposed previously by us, is supported by the present SEIRAS data as the
"detoxification mechanism", featured by an increased mobility of the adsorb
ed CO with suppressed coverage.