Supported Gold Nanoparticles as Catalysts in Peroxidative and Aerobic Oxidation of 1-Phenylethanol under Mild...

The efficiency of Au/TiO₂ based catalysts in 1-phenylethanol oxidation was investigated. The role of support modifiers (La₂O₃ or CeO₂), influence of gold loading (0.5% or 4%) and redox pretreatment atmosphere, catalyst recyclability, effect of oxidant: tert-butyl hydroperoxide (TBHP) or O₂, as well as the optimization of experimental parameters of the reaction conditions in the oxidation of this alcohol were studied and compared with previous studies on 1-octanol oxidation. Samples were characterized by temperature-programmed oxygen desorption (O₂-TPD) method. X-ray photoelectron spectroscopy (XPS) measurements were carried out for used catalysts to find out the reason for deactivation in 1-phenylethanol oxidation. The best catalytic characteristics were shown by catalysts modified with La₂O₃, regardless of the alcohol and the type of oxidant. When O₂ was used, the catalysts with 0.5% Au, after oxidative pretreatment, showed the highest activity in both reactions. The most active catalysts in 1-phenylethanol oxidation with TBHP were those with 4% Au and the H₂ treatment, while under the same reaction conditions, 0.5% Au and O₂ treatment were beneficial in 1-octanol oxidation. Despite the different chemical nature of the substrates, it seems likely that Au⁺(Au^δ+) act as the active sites in both oxidative reactions. Density functional theory (DFT) simulations confirmed that the gold cationic sites play an essential role in 1-phenylethanol adsorption.