Photocatalytic nitric oxide (NO) decomposition and reduction reactions, using carbon monoxide (CO) as a reducing gas, have been investigated over Degussa P25 titanium dioxide photocatalysts, using a continuous flow reactor. The effects of thermal pretreatment temperature and reaction gas composition on the activity and selectivity of the decomposition and reduction reactions have been evaluated. Prepared materials were characterised by X-ray diffraction (XRD), N-2 physisorption, transmission electron microscopy (TEM) and differential scanning calorimetry (DSC) and findings from these techniques were used to explain the observed photocatalytic properties. XRD and TEM results indicated that for the pretreatment temperatures used (70, 120, 200,450 and 600 degrees C) there was no appreciable change in the phase composition and the original composition of ca. 77 vol.% anatase and 23 vol.% rutile was maintained even after treatment at 600 degrees C. It was found that the photocatalytic activity for both the decomposition and reduction reactions decreased with increasing pretreatment temperature. This was attributed to the removal of surface hydroxyl species that act as active sites for reaction. For the decomposition reactions the only products observed were nitrogen and nitrous oxide and the selectivity for nitrogen formation remained constant (ca. 23%) regardless of the pretreatment temperature. The presence of CO in the reaction gas had a dramatic effect on the selectivity of the reactions with nitrogen selectivities as high as 65% being observed. It was found that as the CO/NO ratio increased the selectivity for nitrogen formation increased. (c) 2005 Elsevier B.V. All rights reserved.