0000000000219460
AUTHOR
Tapio Salmi
Oxidative dehydrogenation of alcohols on gold : An experimental and computational study on the role of water and the alcohol chain length
The oxidative dehydrogenation of primary alcohols promoted by gold nanoparticles was investigated from an experimental and computational viewpoint to derive a plausible reaction mechanism and to understand the role of water and alcohol chain length in the elementary steps. The influence of water in reaction kinetics and product distribution was determined in a laboratory-scale microreactor adding water to the reaction mixture in different amounts. DFT calculations revealed that the presence of water on the catalyst surface is beneficial to assist the key step in alcohol oxidation i.e., oxygen activation by protonation. The calculations were performed for primary alcohols ranging from methan…
Kinetic Modeling of Ethyl Benzoylformate Enantioselective Hydrogenation over Pt/Al2O3
A kinetic model was developed for the enantioselective hydrogenation of ethyl benzoylformate (EBF) on a modified Pt/Al2O3 catalyst. This model was based on the assumption of different numbers of si...
Oxidative Dehydrogenation of Ethanol on Gold : Combination of Kinetic Experiments and Computation Approach to Unravel the Reaction Mechanism
Abstract Selective alcohol dehydrogenation on heterogeneous catalysts is a key industrial reaction for production of aldehydes, ketones, and carboxylic compounds. Design of catalysts with improved activity and selectivity requires understanding of the reaction mechanism and kinetics. Herein, experiments, density functional theory (DFT) and kinetic modelling were combined to elucidate the mechanism and kinetics of ethanol oxidative dehydrogenation to acetaldehyde on gold catalysts. Catalytic experiments clearly emphasized the role of oxygen in this reaction. Ethanol conversion was rather independent on the gold cluster size. Formation of minor products, acetic acid and ethyl acetate was stru…
Kinetics of homogeneous catalytic chlorination of acetic acid
The kinetics of the chlorination of acetic acid (HAc) to monochloroacetic acid (MCA) and the physical solubility of chlorine in HAc and its mixtures with MCA were investigated in a laboratory scale semibatch reactor. The temperature dependence of the Henry's constant was determined from solubility data obtained at temperatures between 70°C and 110°C. The kinetic experiments were performed at 75–100°C with 3–13 mol % acetyl chloride (AcCl) and 0–5 weight % H2SO4 added as catalysts. Gas chromatography was used to determine the concentrations of HAc, MCA, dichloroacetic acid and AcCl during the experiments. The results indicate that the reaction rate is independent of the concentrations of HAc…