Abstract

Abstract The electroadsorption of CO on a Ni electrode was studied by cyclic voltammetry and Potential-Modulated Reflectance (PMR) Spectroscopy. A maximum at about 265 nm, and a broad band at 370 nm, appeared in the PMR spectrum of CO chemisorbed on Pt. According to a previous hypothesis, this would indicate that the CO molecule is chemisorbed in an on-top position. The intensity of the PMR signals at 265 and 370 nm of chemisorbed CO increased linearly with the modulation amplitude, as corresponds to a true electroreflectance effect, i.e. the PMR signal was not due to a faradaic change of the oxidation state of the surface. The assignment of the PMR maxima at 265 and 370 nm to chemisorbed CO was unequivocally proved by several tests, including reflectograms in which the PMR signal intensity at 265 nm was recorded during a slow cyclic potential sweep, so that the intensity of the PMR signal could be correlated with the current in the cyclic voltammogram.

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