The targeted design of new catalyst materials can only be accomplished once a fundamental understanding of the interactions between material surfaces and adsorbed molecules is developed. In situ infrared spectroscopy and mass spectrometry methods were employed to probe interactions at the gas-surface interface of oxide-supported metal nanoparticle materials. High vacuum conditions allowed for systematic investigations to describe detailed reaction mechanisms. Specifically, variable temperature infrared spectroscopy was utilized to uncover the binding energetics of CO to the oxide surface of TiO2-based materials. As binding energetics are related to the electronic structure of the adsorption site, differences in evaluated binding enthalpies are hypothesized to probe electronic metal-support interactions that describe charge transfer between the supported metal nanoparticles and TiO2. Cu/TiO2 aerogels were identified as a candidate for more in-depth studies. Flow reactor methods in combination with the surface-based infrared spectroscopy were utilized to elucidate the CO oxidation reaction mechanism over Cu/TiO2 aerogels. Bridging oxygen atoms on TiO2 regions of the material were identified as the active site for catalysis in a Cu-assisted Mars-van Krevelen lattice extraction mechanism. Methanol oxidation was then studied with similar methods to show the complete conversion to CO2 and H2O at high temperatures through the reduction of titania and formation of a formate intermediate. Higher-order carbonaceous alcohols were probed for adsorption and reactivity on Cu/TiO2 aerogels and were observed to follow a similar reaction pathway. The higher-order alcohols, however, were shown to undergo a partial oxidation pathway in the absence of gaseous O2 that is hypothesized to originate from enhanced binding to Cu sites. The decomposition of the chemical warfare agent simulant dimethyl chlorophosphate was also investigated. A hydrolysis pathway to form the significantly less toxic molecule CH3Cl was observed, highlighting the unique promotional effects and chemistry on Cu/TiO2 aerogels. The results presented exemplify both the influence of electronic metal-support interactions on catalysis and the versatile reactivity of Cu/TiO2 aerogels.