Methanol oxidation as probe reaction for active sites in Au/ZnO and Au/TiO2 catalysts

The catalytic activity was found to be correlated with the number of Au atoms at the perimeter of the Au nanoparticles suggesting that oxygen activation occurs at their perimeter and the oxide provides methoxy species reacting at the interface. [Display omitted] ► Methanol oxidation was investigated over metal oxide-supported Au nanoparticles. ► Smaller Au particles or a higher number of small Au particles enhance the activity. ► Methoxy species adsorbed on the oxide support are identified as intermediates. ► The activity correlates with the number of Au atoms at the perimeter. ► Oxygen activation takes place at the perimeter of the Au nanoparticles. Methanol oxidation was used as test reaction to investigate the influence of the metal, of the support, and of metal-support interactions in Au/ZnO and Au/TiO2 catalysts. Catalytic measurements as well as infrared spectroscopy were applied under continuous flow conditions in fixed-bed reactors. A strong effect of the Au loading ranging from 0.6wt.% to 1.9wt.% was found for both Au/ZnO and Au/TiO2 catalysts with Au particle sizes in the range from 3 to 7nm. Methanol combustion yielding H2O and CO2 was the main reaction path, but also reactions such as partial oxidation of methanol, steam reforming of methanol, methanol decomposition as well as the selective oxidation of methanol to methyl formate, formaldehyde, or dimethoxymethane were found to occur. Smaller Au particles and a higher amount of small Au particles had a beneficial effect on the activity. Infrared spectroscopy identified methoxy species adsorbed on the metal oxides as intermediates in methanol oxidation. The product distribution was found to depend on the oxide used as support due to the different Lewis acidities. On Au/TiO2, strongly bound formates acted as reversible catalyst poison. The catalytic activity was found to be correlated with the number of Au atoms at the perimeter of the Au nanoparticles. Correspondingly, oxygen activation is assumed to occur at their perimeter, and the oxide provides methoxy species reacting at the interface.