The gas phase thermo-photo production of hydrogen from methanol:water mixtures was tested using platinum ceria-titania ternary solids. This contribution focusses on the analysis of the role of ceria and the usefulness of combining heat and light sources in order to boost catalytic activity. To this end, we provide a quantitative assessment of thermo-photo activity as well as a detailed characterization of the catalytic solids with emphasis in the use of in-situ X-ray absorption and infrared spectroscopies. The adequate combination of components in the platinum ceria-titania ternary system renders highly active and stable catalysts, maximizing hydrogen production (rate of ca. 45 mmol g(-1)h(-1)) for a solid having a 1/2.5 wt% of platinum/ceria supported on titania. The characterization shows that this occurs through a synergetic effect among components of the solids and takes place with a critical role of defects located at the ceria-titania interface and the noble metal component. The cooperative action between components promotes the evolution of specific carbon-containing intermediates (related to the step-wise hole-triggered oxidation of the methanol molecule, decarbonylation of intermediates and the water gas shift) and the concomitant production of hydrogen..
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