S K-edge NEXAFS has bean used to monitor the thermally-activated react
ion of SO2 with TiO2(100)-(1x3) and TiO2(100)-(1x1) in order to invest
igate the influence of surface structure and oxygen vacancies on the r
eactivity. In each case SO2 chemisorbs at 110 K, reacting further to f
orm a sulphite-like intermediate species at higher temperatures (110-4
00 K). This intermediate transforms to a sulphate-like species as the
temperature is further increased (130-500 K). The polarisation depende
nce of the NEXAFS for the sulphate-like species on both substrates at
130-220 K evidences a lowering of the expected T-d molecular symmetry.
Overall, the data indicate that the mesoscopic morphology of the subs
trate has little influence on the adsorption site or reaction pathway
for SO2. In addition, the only discernable effect of oxygen vacancies
on the reaction is that 0.03 ML of sulphide is formed on TiO2(100)-(1x
3) following SO2 exposure.