Adsorption and photo-oxidation of acetaldehyde on TiO2 and sulfate-modified TiO2: Studies by in situ FTIR spectroscopy and micro-kinetic modeling

Adsorption and photocatalytic oxidation of acetaldehyde have been investigated on TiO2 and sulfate-modified TiO2 films (denoted SO4single bondTiO2). In situ Fourier transform infrared spectroscopy was used to study surface reactions as a function of time and number of experimental cycles. Spectral analysis and micro-kinetic modeling show that crotonaldehyde formation occurs spontaneously on TiO2 but is impeded on SO4single bondTiO2, where instead acetaldehyde desorption is significant. Photo-oxidation yields significant amounts of formate on TiO2 and was identified as the rate-determining step and associated with site blocking. Significantly smaller amounts of formate were observed on SO4single bondTiO2, which is due to the acidity of this surface resulting in weaker bonding of aldehyde and carboxylate intermediate species. Our results are of considerable interest for applications to photocatalytic air purification and to surfaces with controlled wettability.