Effect of Gold Electronic State on the Catalytic Performance of Nano Gold Catalysts in n-Octanol Oxidation

This study aims to identify the role of the various electronic states of gold in the catalytic behavior of Au/M_xO_y/TiO₂ (where M_xO_y are Fe₂O₃ or MgO) for the liquid phase oxidation of n-octanol, under mild conditions. For this purpose, Au/M_xO_y/TiO₂ catalysts were prepared by deposition-precipitation with urea, varying the gold content (0.5 or 4 wt.%) and pretreatment conditions (H₂ or O₂), and characterized by low temperature nitrogen adsorption-desorption, X-ray powder diffraction (XRD), energy dispersive spectroscopy (EDX), scanning transmission electron microscopy-high angle annular dark field (STEM HAADF), diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy of CO adsorption, temperature-programmable desorption (TPD) of ammonia and carbon dioxide, and X-ray photoelectron spectroscopy (XPS). Three states of gold were identified on the surface of the catalysts, Au⁰, Au¹⁺ and Au³⁺, and their ratio determined the catalysts performance. Based on a comparison of catalytic and spectroscopic results, it may be concluded that Au⁺ was the active site state, while Au⁰ had negative effect, due to a partial blocking of Au⁰ by solvent. Au³⁺ also inhibited the oxidation process, due to the strong adsorption of the solvent and/or water formed during the reaction. Density functional theory (DFT) simulations confirmed these suggestions. The dependence of selectivity on the ratio of Brønsted acid centers to Brønsted basic centers was revealed.