Gas-phase photocatalytic activity of sputter-deposited anatase TiO2 films: Effect of 〈001〉 preferential orientation, surface temperature and humidity

We present a systematic in situ study of the environmental reaction conditions on the photocatalytic activity of sputter deposited anatase TiO2 films with controlled amounts of preferential 〈001〉 orientation. In particular, the effects of relative humidity (RH) and substrate temperature (Tsurf) are investigated. It is found that {001} facets, which are present in higher abundance on highly oriented samples, exhibit an order of magnitude higher reactivity for gas-phase photocatalytic oxidation of the indoor air pollutant acetaldehyde (CH3CHO) than {101} facets do, and a functional dependence of the reaction rate on facet orientation is determined. It is proposed that water adsorbed on the film contributes to two counteracting effects on the photocatalytic activity: (i) It provides hole acceptors to complete the photo-induced redox cycle and subsequent OH radical formation for pollutant degradation, and (ii) it creates a diffusion barrier between the catalyst interface and pollutant molecules adsorbed in the water layer. As a consequence, increasing Tsurf at high RH has the beneficial effect of removing excess water and reducing the diffusion barrier, thereby improving the photocatalytic activity. A comparison is also made with a commercial anatase TiO2 film, with less developed surface crystallinity and random facet distribution, where the improvement is even more pronounced. Films with a higher degree of orientation exhibit much more stable performance over a range of operating conditions, which suggests that it is possible to tune the effects of water and exposed facet orientation to achieve optimum activity and make TiO2 films amenable to a larger (RH, Tsurf) parameter space for practical applications.