Nonlinear vibrational spectroscopic studies of molecular interaction and charging behavior at solid/liquid interfaces

Solid-liquid interfaces have been the focus of different communities of scientists due to its importance in industrial applications and chemical processes in nature. Molecular interactions and surface charges affect the physicochemical properties of these interfaces and a thorough understanding is still lacking now. This thesis describes our work in studying several model solid-liquid interfaces using sum-frequency vibrational spectroscopy. Through the studies of interfacial vibrational spectra, we hope to gain better understanding of molecular interactions in competitive adsorption process and also surface charging behavior at different pH and salt concentrations.;We start by studying alcohol-water mixture and the adsorption behavior at both hydrophilic and hydrophobic surfaces. In both cases, alcohol adsorbs preferentially from water. The tendency for water to form strong hydrogen-bonding network is the driving force for preferential adsorption of alcohol. We proposed two different interfacial molecular structures on hydrophilic and hydrophobic surfaces. We move on to study the interaction of pure water with a solid surface. Single crystal alumina is used as a model system. At different pH, the surface can undergo protonation and deprotonation reactions and accumulates surface charge. Both the hydrogen-bonding with water and the surface field created by surface charge can affect interfacial water structure. Combining the information obtained with intensity and phase spectra, we find water molecules have two types of bonding within the interfacial layer: weakly hydrogen-bonded species near 3450 cm-1 that does not flip with switching surface charge, and strongly hydrogen-bonded species at 3200 cm-1 that readily flips with switching surface field. One other system we have studied is nanoporous silica-water interface. We found that signal from interfacial water is reduced due to the porous nature of the film. The water spectral features tell us about the interfacial bonding environment and we found close relation of spectra features with surface morphology and surface silane coverage. Finally we studied the surface hydroxylation reaction of different crystalline alumina planes and its dependence on thermal-treatment history of the surface. The results indicate that upon hydroxylation, each crystal plane has distinct OH stretching vibrations that depend mainly on thermal-treatment temperature rather than other factors.