Ethanol degradation by TiO2 and TiO2 doped with Fe, Pd and Cu has undergone FTIR spectroscopic study. Ethanol interaction with bare-TiO2 and Fe-TiO2 yields the formation of ethoxides on the catalyst surface that can readily be oxidised to acetates by radicals O-2(.-) and (OH)-O-.. Conversely, ethanol interaction with Pd-TiO2 and Cu-TiO2 generates an intermediate species between ethanol and ethyleneglycol. Acetate-producing oxidation of these latter species is inhibited because electrons that form radicals O-2(.-) are captured by the respective metallic oxides. In these catalysts a degradation mechanism based on ethanol reaction with photogenerated holes is proposed. Also, different surfacial OH distributions determine ethanol-catalyst interactions. Furthermore, ethanol degradation has been studied in a gaseous continuous flow system. Exhaust gases have been analysed by means of GC and FTIR. These experiments demonstrate that bare-TiO2 and Fe-TiO2 degrade ethanol to provide only acetaldehyde and their catalytic activity progressively decays over time. On the contrary, Pd-TiO2 and Cu-TiO2 have produced ethyleneglycol in addition to acetaldehyde. No deactivation of these catalysts was observed during the experimental time period (6 h). (C) 2004 Elsevier B.V. All rights reserved.