Surface-Enhanced Infrared Absorption Spectroscopic Studies of Adsorbed Nitrate, Nitric Oxide, and Related Compounds 1: Reduction of Adsorbed NO on a Platinum Electrode

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Abstract
Surface-enhanced infrared absorption spectroscopy (SEIRA) was used to examine the adsorption state of nitrogen monoxide (nitric oxide, NO) and the reduction of the adsorbed species. The SEIRA spectra gave two distinct bands at 1723−1733 and 1575−1607 cm-1 with an additional weak band at 1656−1676 cm-1 at 0.20 V, the frequencies of which are slightly dependent on the surface coverage. The former two bands are attributed to the on-top and bridged NO, respectively. While the on-top NO stably remained on the surface in the potential range of 0.05 −0.60 V, the bridged NO decreased in its intensity with increasing electrode potential. The reduction of the adsorbed NO obeys first-order kinetics with respect to the adsorbed NO. The rate constants are 2.24 ± 0.03 and 0.24 ± 0.09 s-1 at −0.10 V for the on-top and bridged NO, respectively. Tafel slopes obtained from the potential dependence of the rate constant indicate that the rate-determining step is the first electron-transfer process.

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