XPS and FTIR investigations of the transient photocatalytic decomposition of surface carbon contaminants from anatase TiO2 in UHV starved water/oxygen environments

This paper explores the transient photocatalytic oxidation mechanism of carbon contaminants from a high surface area anatase TiO2 pellet under starved water/oxygen reaction conditions created when specimens are irradiated via a 375 nm UV laser inside the UHV analysis chamber of an XPS spectrometer. Complementary results are also provided following similar UV irradiations and reaction procedures in an evacuated in situ reaction cell of a Fourier-transform infrared spectrometer (FTIR). An interactive and non-steady state transient photocatalytic reaction is observed between surface carbon species and strongly adsorbed H2O brought to the exterior surface of the pellet via UV photodesorption from within the deeper lying pores of the pellet. The reaction stoichiometry and quantum efficiency of the reaction are reported at various irradiation intensities. In situ FTIR spectral features are also presented and discussed for a non-UV treated TiO2 sample and a 2-hour UVtreated TiO2 sample under evacuated conditions also showing the decomposition of carbon contaminants species and the consumption of adsorbed water/hydroxyls with the ensuing formation of carboxyl (HO-C--O) carbon species and isolated surface hydroxyls. The photocatalytic decomposition of carbon species and the concomitant consumption of oxygen containing species was also tracked by following the XPS spectral changes of a UV-irradiated area on the pellet surface compared to a dark reference spot on the same specimen. Eight different reaction cases at four different UV intensities, repeated twice each, were also investigated using separate pieces of the same TiO2 media. The measured stoichiometry for the decomposition of carbon species and consumption of oxygen ranged from 0.53 during the first 10-20 min of irradiation and increased to 0.65 with an average value of 0.59 and a standard deviation of 0.11. These data suggest that the reaction product and leaving group from the TiO2 surface is primarily CO2 during the first 10-20 min of initial reaction with perhaps a small fraction of CO toward the end of reaction. Heating the sample specimen to 100 degrees C for 2-hour inside the XPS-UHV analysis chamber prior to UV illumination was effective in eliminating photocatalytic oxidation and carbon removal from the surface thereby demonstrating that strongly adsorbed water (prior to heating in vacuum) was a critical and limiting reagent in the overall H2O transport and reaction process. Photon efficiencies for the reaction were calculated based on the number of carbon species removed from the XPS-observable surface versus the number of the UV photons adsorbed in the topmost 2 nm of the sample. The highest photon efficiency observed was 0.0186 after 5-10 min of UV exposure at 1.5 mW/cm2. All reaction cases showed a significant efficiency drop after 30 min of UV irradiation due to the consumption of the adsorbed reactants, both carbon and water. From detailed deconvolution of the XPS C 1s spectra, UV irradiation showed a high selectivity towards hydrocarbon contaminant decomposition, which was 75% +/- 5% of all carbon species removed.