The emphasis in the present study was placed on developing Raman spectroscopy into a versatile technique, whichoffers intriguing opportunities for investigating electrocatalytic reaction. Through the in-situ Raman spectroscopicstudy, with a confocal Raman microscope, on the methanol electrooxidation on platinum electrodes with varioussurface roughness, it has shown the advantage in obtaining the informative spectra during the surface reaction withhigh faradaic current. This is hard to be performed by the other spectroscopic methods that have to use the thin-layercell. The ability to obtain both the low frequency and the high frequency vibrations of Pt-C and C O bands allowsthe assignment of surface species unambiguously. The ease of studying the surface bonding, investigating highlyroughened surfaces with dark color and using high concentration electrolyte may provide a way to bridge the gapbetween the systems of fundamental research and practical applications. The results reveal the surface roughnesseffect on the electrooxidation process and provide clear evidence for the parallel oxidation mechanism.

A Raman cell suitable for the study of solid/liquid/gas three-phase systems and that can work very efficiently onconfocal microprobe Raman systems was introduced. The influence of the environment on the adsorption behavior ofmodel molecule CO on Pt was investigated and different behaviors were observed in the aqueous solution compared tothe gas phase. A preliminary Raman measurement on the three-phase system was performed using methanol as a testingsolution. The diffusion of CO, a dissociate product of methanol, on the Pt electrode from the solution side to the gasside was observed.

We describe a method of preparing gold scanning tunneling microscopy STM tips by direct currentelectrochemical etching in concentrated HCl and ethanol solution. Gold tips with tip apex radiuslower than 30nm can be reproducibly prepared by this method. The influence of the solutioncomposition, etching voltage on the surface structure, and sharpness has been investigated. Thesetips can be efficiently used for STM imaging, tip-enhanced Raman spectroscopy, and light emissioninvestigations on the same sample.

The surface Raman study of the electrode potential effect on the adsorption behavior of cyanide on the Pt surface wasperformed on a confocal microprobe Raman system with the help of a special surface pretreatment for the platinumelectrode. The abrupt change of the dependence of the CNy stretching vibration on the potential at ca. y0.6 V indicates asubtle orientation change of the adsorbed CN. This is supported by the changes of the Pt-C vibration located at ca. 400cmy1. A detailed discussion is given on the potential dependent adsorption behavior and the frequency shift of the majorvibrational bands.