Effect of the Microstructure of the Semiconductor Support on the Photocatalytic Performance of the Pt-PtO(x)/TiO(2) Catalyst System

The influence of the semiconductor microstructure on the photocatalytic behavior of Pt-PtO(x)/TiO(2) catalysts was studied by comparing the methanol-reforming performance of systems based on commercial P25 or TiO(2) from sol–gel synthesis calcined at different temperatures. The Pt co-catalyst was deposited by incipient wetness and formed either by calcination or high-temperature H(2) treatment. Structural features of the photocatalysts were established by X-ray powder diffraction (XRD), electron spin resonance (ESR), X-ray photoelectron spectroscopy (XPS), optical absorption, Raman spectroscopy and TEM measurements. In situ reduction of Pt during the photocatalytic reaction was generally observed. The P25-based samples showed the best H(2) production, while the activity of all sol–gel-based samples was similar in spite of the varying microstructures resulting from the different preparation conditions. Accordingly, the sol–gel-based TiO(2) has a fundamental structural feature interfering with its photocatalytic performance, which could not be improved by annealing in the 400–500 °C range even by scarifying specific surface area at higher temperatures.