Gold catalysed selective oxidation of alcohols in supercritical carbon dioxide

The oxidation of benzyl alcohol to benzaldehyde over different supported gold catalysts in supercritical carbon dioxide has been investigated in a high-pressure batch reactor. Only molecular oxygen was used as oxidant and no base was needed. Different supports and preparation methods for the catalysts were tested and parameters like reaction temperature, pressure and molar ratios of the components were varied to study the catalytic behaviour. Gold colloids deposited on a titania support (1%Au/TiO2) yielded a conversion of 16.0% after 3h and a high selectivity to benzaldehyde of 99% under single-phase conditions. The reaction rate was significantly higher than in a corresponding "solvent-free” reaction without CO2. Even higher rates were found when a CO2-expanded phase was present. Monitoring of the oxidation in a high-pressure view cell via infrared transmission spectroscopy unravelled a slowdown of the reaction rate above 15% conversion. In addition, 1-octanol and geraniol were oxidised as well under similar conditions, yielding conversions of 4% and 10%, respectively, with selectivities towards octanal and geranial of 90% and 30%. Thus, the combined application of gold-based catalysts and supercritical CO2 offers an interesting alternative to the known methods of alcohol oxidatio

Probing Active Sites During Palladium-Catalyzed Alcohol Oxidation in "Supercritical” Carbon Dioxide

Structural information has been gained during aerobic benzyl alcohol oxidation in "supercritical” carbon dioxide at 150 bar on alumina-supported palladium by X-ray absorption spectroscopy while monitoring simultaneously the performance of the catalyst. The reduction of the catalyst by benzyl alcohol could be monitored by the analysis of the near-edge region of the Pd K-edge. The palladium constituent was mainly in metallic state under operating conditions. Partial reoxidation was observed when only oxygen in "supercritical” carbon dioxide in the absence of alcohol was fed. The catalytic activity of the PdOx/Al2O3 catalyst during benzyl alcohol oxidation was comparable to that in a conventional continuous fixed-bed reactor and depended on the oxygen concentration in the feed. The rate of alcohol conversion went through a maximum when the oxygen concentration was increased. At maximum rate, part of the palladium was in the oxidized state. Upon further increase of the oxygen concentration, the activity decreased because of the formation of surface palladium oxide. The reaction rate in "supercritical” carbon dioxide was strikingly higher than that observed for the corresponding liquid-phase oxidatio

Insights into the Structural Dynamics of Pt/CeO2_{2} Single-Site Catalysts during CO Oxidation

Despite their high atomic dispersion, single site catalysts with Pt supported on CeO$_{2}$ were found to have a low activity during oxidation reactions. In this study, we report the behavior of Pt/CeO$_{2}$ single site catalyst under more complex gas mixtures, including CO, C$_{3}$H$_{6}$ and CO/C$_{3}$H$_{6}$ oxidation in the absence or presence of water. Our systematic operando high-energy resolution-fluorescence-detected X-ray absorption near-edge structure (HERFD-XANES) spectroscopic study combined with multivariate curve resolution with alternating least squares (MCR-ALS) analysis identified five distinct states in the Pt single site structure during CO oxidation light-off. After desorption of oxygen and autoreduction of Pt$^{4+}$ to Pt$^{2+}$ due to the increase of temperature, CO adsorbs and reduces Pt$^{2+}$ to Pt$^{δ+}$ and assists its migration with final formation of Pt$_{x^Δ+}$ clusters. The derived structure–activity relationships indicate that partial reduction of Pt single sites is not sufficient to initiate the conversion of CO. The reaction proceeds only after the regrouping of several noble metal atoms in small clusters, as these entities are probably able to influence the mobility of the oxygen at the interface with ceria