LAUSR

Abstract The effect of Pt deposition on TiO2 and of Pt particle size on the photocatalytic steam reforming of methanol was studied by in situ attenuated total reflectance infrared spectroscopy (ATR-IR). Two 0.5 wt.% Pt/TiO2 samples were investigated, one possessing Pt nanoparticles of ca. 4 nm mean size, the other Pt clusters of ca. 1.3 nm mean size showing significantly different photoactivity in terms of both hydrogen production rate and selectivity to CO, CO2 and all other by-products. The presence of Pt nanoparticles strongly affected both the adsorption/desorption and the reactivity properties of the TiO2 surface. Moreover, the variation of the IR spectrum background upon UV–vis irradiation proved that the photopromoted electrons can be trapped by the Pt particles with the consequent increase of electron-hole separation. Reducing the Pt size from nanoparticles to clusters increased the rate of methanol and water absorption and hindered the detrimental formation of irreversibly adsorbed CO on Pt. All of these aspects contribute to increase the photocatalytic performance of Pt cluster-decorated TiO2 with respect to Pt nanoparticles containing TiO2. Finally, prolonged exposure of all samples to methanol/water vapour in the dark led to the formation of unreactive formate which persisted also under UV–vis irradiation. By contrast, this spectator species did not form when the sample was exposed to methanol/water vapour under UV–vis irradiation.