Normal and Enhanced Raman Spectroscopy of Carbon Electrode Surfaces

This thesis discusses the relationship between the microstructure and the electrochemical properties of carbon electrodes. First, a near infrared Raman spectrometer with a diode laser coupled to a charge coupled device was developed to overcome intrinsic limitations in the Raman scattering process. The spectrometer was evaluated in sensitivity, limit of detection, dynamic range, and fluorescence rejection ability. The experimental results indicate that this spectrometer is more sensitive than the existing FT -Raman technique and provides a viable alternative for near infrared region Raman techniques. This system was then applied in a comprehensive Raman study of the vibrational microstructure of several carbon electrodes over a wide incident laser wavelength region. Based on a lattice dynamics model, a wide range of experimental data were used to clarify the controversy of the Raman feature at ca. 1350 cm^{ -1} (D band). It has been attributed to an intrinsic lattice vibration mode which becomes active if the wavevector selection rule breakdowns. Further, the laser wavelength dependent effect of the D band position and relative intensity was investigated. Four vibrational modes were discovered and assigned to lattice vibration modes. The assignment was assisted by their laser wavelength position dependence. Finally, to better understand the relationship between the surface microstructure and the electrochemical properties, a surface enhanced Raman scattering technique was developed and applied. In this technique, the carbon surfaces were studied through electrochemically depositing silver in situ on the carbon electrode surface. The technique was proven to be surface sensitive and applied to the study of many modified carbon electrodes. The experimental results provide strong evidence to link electrochemical activity of carbon electrodes with grain boundaries or defects in the microstructure of the electrodes. With this knowledge a better understanding of carbon electrode manufacture and design can be obtained.