Synthesis of photocatalytic TiO2 nano-coatings by supersonic cluster beam deposition

In this paper we report on the photocatalytic behavior in gas phase propane oxidation of well-defined TiO2 nanoparticle (NP) coatings prepared via Supersonic Cluster Beam Deposition (SCBD) on Si-wafers and quartz substrates. The temperature dependent crystal phase of the coatings was analyzed by Raman spectroscopy, and the morphology by High Resolution-Scanning Electron Microscopy. SCBD deposition in the presence of oxygen enables the in situ synthesis of TiO2 layers of amorphous NP at room temperature. Adapting the deposition temperature to 500 degrees C or 650 degrees C leads to Anatase crystals of variable size ranges, and layers showing significant porosity. At 800 degrees C mainly Rutile is formed. Post annealing by wafer heating of the amorphous NP prepared at room temperature results in comparable temperature dependent phases and morphologies. Photocatalytic activity in propane oxidation was dependent on the morphology of the samples: the activity decreases as a function of increasing particle size. The presence of water vapor in the propane feed generally increased the activity of the wafer-heated samples, suggesting OH groups are not profoundly present on SCBD synthesized layers. In addition, a remarkable effect of the substrate (Si or Quartz) was observed: strong interaction between Si and TiO2 is largely detrimental for photocatalytic activity. The consequences of these findings for the application of SCBD to synthesize samples for fundamental (spectroscopic) study of photocatalysis are discussed. (C) 2013 Elsevier B.V. All rights reserved.