4.6 Article

Steering the Selectivity in Gold-Titanium-Catalyzed Propene Oxidation by Controlling the Surface Acidity

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JOURNAL OF PHYSICAL CHEMISTRY C
卷 125, 期 30, 页码 16557-16568

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AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.1c05503

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  1. Utrecht University

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Supported nanoparticulate Au/Ti-SiO2 catalysts show promise in selective epoxidation of propene, with the selectivity being controlled by altering the acidity of the surface titanol groups. The presence of Na+ and acidic Ti-sites plays a crucial role in determining the selectivity towards propene oxide or propanal.
Supported nanoparticulate Au/Ti-SiO2 catalysts are a promising candidate for selective epoxidation of propene with H-2/O-2 mixtures. Here, we demonstrate that by altering the acidity of the surface titanol groups in Au/Ti-SiO2, the selectivity of these catalysts in propene oxidation can be controlled. That is, Au/Ti-SiO2 prepared using an alkali base during gold deposition shows basic properties due to the formation of Ti-ONa groups. The catalysts that contained Na+ and neutralized acid sites demonstrate high selectivity toward propene oxide. On the contrary, when the acidity of the Ti-OH groups is preserved by using NH4OH as a base during gold deposition, the catalyst is highly selective toward propanal at a similar propene conversion. This difference in selectivity is explained by the isomerization of initially formed propene oxide into propanal over acidic Ti-OH groups as we demonstrated using stacked bed experiments, where the Ti-support was exposed to propene oxide. When Na+ was present, no isomerization was observed, while without Na+ present, propene oxide was isomerized to propanal. In short, we demonstrate the crucial role of Na+ and acidic Ti-sites in steering the selectivity in gold-catalyzed propene epoxidation.

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