Studies of adsorption of α,β-unsaturated carbonyl compounds on heterogeneous Au/CeO, Au/TiO and Au/SiO catalysts during reduction by hydrogen.

Our research focuses on phenomena accompanying adsorption of mesityl oxide (4-methylpent-3-en-2-one) on the surface of heterogeneous supported gold catalysts: Au/CeO, Au/TiO and Au/SiO. We have studied reduction in the gas phase of (volatile) α,β-unsaturated carbonyl compounds (R-(V)ABUCC) which mesityl oxide is a basic model of. infrared (IR) spectroscopy was employed to establish that the most active catalysts allow adsorption of conjugated ketones or aldehydes in the enolate ( bridge-like adsorption through the oxygen from the carbonyl group and the β-carbon) and carboxylic form or with the C[double bond, length as m-dash]C double bond on a Lewis acidic site. Reductive properties of the catalysts and pure supports were studied by temperature-programmed reduction (TPR). We show that cerium(iv) oxide (CeO, ceria) and titanium(iv) oxide (TiO, titania) when decorated with gold nanoparticles (AuNP) can interact with hydrogen at temperatures approx. 150 °C lower than typical for pure oxides what includes even cyclic adsorption and instant release of H below 100 °C in the case of gold-ceria system. Morphology and structure characterisation by transmission electron microscopy (TEM) and powder X-ray diffraction (PXRD) confirms that, with the obtained Au loadings, we achieved excellent dispersion of AuNPs while maintaining their small size, preferably below 5 nm, even though the Au/CeO catalyst contained broad distribution of AuNPs sizes.