We have investigated the adsorption and reaction of methanol with Au/TiO2 catalysts using a pulsed flow reactor, DRIFTS and TPD. The TiO2 (P25) surface adsorbed a full monolayer of methanol, much of it in a dissociative manner, forming methoxy groups associated with the cationic sites, and hydroxyl groups at the anions. The methoxy is relatively stable until 250 °C, at which point decomposition occurs, producing mainly dimethyl ether by a bimolecular surface reaction. As the concentration of methoxy on the surface diminishes, so the mechanism reverts to a de-oxygenation pathway, producing mainly methane and water (at ~330 °C in TPD), but also with some coincident CO and hydrogen. Au catalysts were prepared by the deposition-precipitation method to give Au loadings between 0.5–3 wt %. The effect of low levels of Au on the reactivity is marked. The pathway which gives methane, which is characteristic of titania, remains, but a new feature of the reaction is the evolution of CO2 and H2 at lower temperature (a peak is seen in TPD at 220 °C), and the elimination of the DME-producing state. Clearly this is associated with the presence of Au and appears to be due to the production of a formate species on the surface of the Au component. This formate species is mainly involved in the reaction of methanol with the Au/TiO2 catalysts which results in a combustion pathway being followed, with complete conversion occurring by ~130 °C.
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Nuhu, A., Soares, J., Gonzalez-Herrera, M. et al. Methanol oxidation on Au/TiO2 catalysts. Top Catal 44, 293–297 (2007). https://doi.org/10.1007/s11244-007-0302-z
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DOI: https://doi.org/10.1007/s11244-007-0302-z