Gold catalyzed liquid phase oxidation of alcohol: the issue of selectivity

Commercial carbon nanotubes (CNTs) and carbon nanofibers (CNFs) modified in various ways at the surface have been used as supports for gold nanoparticles (AuNPs) in order to study their influence on the activity/selectivity of catalysts in the aqueous oxidation of alcohol. Particularly oxidative treatment was used to introduce carboxylic functionalities, whereas subsequent treatment with NH3 at different temperatures (473 K, 673 K and 873 K) produced N-containing groups leading to an enhancement of basic properties as the NH3 treatment temperature was increased. The nature of the N-containing groups changed as the temperature increased, leading to an increase in the hydrophobicity of the support surface. Similar Au particle size and similar textural properties of the supports allowed the role of chemical surface groups in both the activity and the selectivity of the reaction of glycerol oxidation to be highlighted. An increase of basic functionalities produced a consistent increase in the activity of the catalyst, which was correlated to the promoting effect of the basic support in the alcoholate formation and the subsequent C-H bond cleavage. The selectivity towards primary oxidation products (C3 compounds) was the highest for the catalysts treated with NH3 at 873 K, which presented the most hydrophobic surface. The same trend in the catalyst activity has been obtained in the aqueous benzyl alcohol base-free oxidation. As in the case of glycerol, the increasing of basicity and/or hydrophobicity increased the consecutive reactions.