Fixation of SO2 molecules on anatase TiO2 surfaces with defects have been investigated by first-principles density functional theory (DFT) calculations and in situ Fourier transform infrared (FTIR) surface spectroscopy on porous TiO2 films. Intrinsic oxygen-vacancy defects, which are formed on TiO2(001) and TiO2(101) surfaces by ultraviolet (UV) light irradiation and at elevated temperatures, are found to be most effective in anchoring the SO2 gas molecules to the TiO2 surfaces. Both TiO2(101) and TiO2(001) surfaces with oxygen vacancies are found to exhibit higher SO2 adsorption energies in the DFT calculations. The adsorption mechanism of SO2 is explained on the basis of electronic structure, charge transfer between the molecule and the surface, and the oxidation state of the adsorbed molecule. The theoretical findings are corroborated by FTIR experiments. Moreover, the (001) surface with oxygen vacancies is found to bind SO2 gas molecules more strongly, as compared to the (101) surface. Higher concentration of oxygen vacancies on the TiO2 surfaces is found to significantly increase the adsorption energy. The results shed new insight into the sensing properties of TiO2-based gas sensors.

Adsorption and photocatalytic oxidation of acetaldehyde have been investigated on TiO 2 and sulphate-modified TiO 2 films (denoted SO 4 -TiO 2 ). 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 modelling show that crotonaldehyde formation occurs spontaneously on TiO 2 but is impeded on SO 4 -TiO 2 , where instead acetaldehyde desorption is significant. Photo-oxidation yields significant amounts of formate on TiO 2 , and was identified as the rate-determining step and associated with site blocking.Significantly smaller amounts of formate were observed on SO 4 -TiO 2 , 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.

Conversion of acetaldehyde to crotonaldehyde on anatase TiO 2 films was studied by in situ Fourier transform infrared spectroscopy (FTIR) and by density functional theory (DFT) calculations. In situ FTIR showed that acetaldehyde adsorption is accompanied by the appearance of a hitherto nonassigned absorption band at 1643 cm -1 , which is shown to be due to acetaldehyde dimers. The results were supported by DFT calculations. Vibrational frequencies calculated within a partially relaxed cluster model for molecular acetaldehyde and its dimer, and for the corresponding adsorbed species on the anatase (101) surface, were in good agreement with experimental results. A kinetic model was constructed based on the combined FTIR and DFT results, and was shown to explain the essential features of the acetaldehyde condensation reaction.

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Photoinduced SO(2) fixation on anatase TiO(2) films was studied by in situ Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS). The TiO(2) films were prepared by reactive DC magnetron sputtering and were subsequently exposed to 50 ppm SO(2) gas mixed in synthetic air and irradiated with UV light at substrate temperatures between 298 and 673 K. Simultaneous UV irradiation and SO(2) exposure between 373 and 523 K resulted in significant sulfur (S) deposits on crystalline TiO(2) films as determined by XPS, whereas amorphous films contained negligible amounts of S. At substrate temperatures above 523 K, the S deposits readily desorbed from TiO(2). The oxidation state of sulfur successively changed from S(4+) for SO(2) adsorbed on crystalline TiO(2) films at room temperature without irradiation to S(6+) for films exposed to SO(2) at elevated temperatures with simultaneous irradiation. In situ FTIR was used to monitor the temporal evolution of the photoinduced surface reaction products formed on the TiO(2) surfaces. It is shown that band gap excitation of TiO(2) results in photoinduced oxidation of SO(2), which at elevated temperatures become coordinated to the TiO(2) lattice through interactions with O vacancies and form sulfite and sulfate surface species. These species makes the surface acidic, which is manifested in nondetectable adherence of stearic acid to the modified surface. The modified films show good chemical stability as evidenced by sonication and repeated recycling of the films. The results suggest a new method to functionalize wide band gap oxide surfaces by means of photoinduced reactions in reactive gases at elevated substrate temperatures. In the case of anatase TiO(2) in reactive SO(2) gas, we here show that such functionalization yields surfaces with excellent oleophobic properties, as probed by adhesion of stearic acid.

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