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

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• 作者：Kevin Kä ; hler ; Marie C. Holz ; Markus Rohe ; Andre C. van Veen ; Martin Muhler ; ^{muhler@techem.rub.de}
• 关键词：Methanol oxidation ; Oxide-supported Au catalysts ; Kinetics ; IR spectroscopy ; Perimeter sites
• 刊名：Journal of Catalysis
• 出版年：2013
• 出版时间：March, 2013
• 年：2013
• 卷：299
• 期：Complete
• 页码：162-170
• 全文大小：1306 K

文摘

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 0.6 wt. % to 1.9 wt. % was found for both Au/ZnO and Au/TiO₂ catalysts with Au particle sizes in the range from 3 to 7 nm. 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.