Exceptional selectivity of LaMnO 3 perovskite supported Au catalysts for the oxidation of glycerol to the dicarboxylate tartronic acid is reported. Through using monometallic Au, Pt or bimetallic Au:Pt nanoparticles the tartronic acid yield could be altered significantly, with a maximum yield of 44% in 6 h with Au/LaMnO 3 and 80% within 24 h. These LaMnO 3 supported catalysts were compared with conventionally TiO 2 supported catalysts, which at comparable reaction conditions produced lactic acid, via a dehydration pathway, in high yield and a maximum tartronic acid yield of only 9% was observed. The LaMnO 3 catalysts produced minimal lactic acid regardless of the supported metal, showing that the support structure influences the prevalence of dehydration and oxidation pathways. The choice of metal nanoparticle influenced product selectivity along the oxidation pathway for both LaMnO 3 and TiO 2 supported catalysts. Au catalysts exhibited a higher selectivity to tartronic acid, whereas AuPt catalysts produced glyceric acid and Pt catalysts produced predominantly C–C scission products. Graphical Abstract

The oxidation of glycerol under alkaline conditions in the presence of a heterogeneous catalyst can be tailored to the formation of lactic acid, an important commodity chemical. Despite recent advances in this area, the mechanism for its formation is still a subject of contention. In this study, we use a model 1 wt. % AuPt/TiO2 catalyst to probe this mechanism by conducting a series of isotopic labeling experiments with 1,3-13C glycerol. Optimization of the reaction conditions was first conducted to ensure high selectivity to lactic acid in the isotopic labeling experiments. Selectivity to lactic acid increased with temperature and concentration of NaOH, but increasing the O2 pressure appeared to influence only the rate of reaction. Using 1,3-13C glycerol, we demonstrate that conversion of pyruvaldehyde to lactic acid proceeds via a base-promoted 1,2-hydride shift. There was no evidence to suggest that this occurs via a 2,1-methide shift under the conditions used in this study.

Gold and gold alloys, in the form of supported nanoparticles, have been shown over the last three decades to be highly effective oxidation catalysts. Mixed metal oxide perovskites, with their high structural tolerance, are ideal for investigating how changes in the chemical composition of supports affect the catalysts' properties, while retaining similar surface areas, morphologies and metal co-ordinations. However, a significant disadvantage of using perovskites as supports is their high crystallinity and small surface area. We report the use of a supercritical carbon dioxide anti-solvent precipitation methodology to prepare large surface area lanthanum based perovskites, making the deposition of 1 wt% AuPt nanoparticles feasible. These catalysts were used for the selective oxidation of glycerol. By changing the elemental composition of the perovskite B site, we dramatically altered the reaction pathway between a sequential oxidation route to glyceric or tartronic acid and a dehydration reaction pathway to lactic acid. Selectivity profiles were correlated to reported oxygen adsorption capacities of the perovskite supports and also to changes in the AuPt nanoparticle morphologies. Extended time on line analysis using the best oxidation catalyst ( AuPt/LaMnO3) produced an exceptionally high tartronic acid yield. LaMnO3 produced from alternative preparation methods was found to have lower activities, but gave comparable selectivity profiles to that produced using the supercritical carbon dioxide anti-solvent precipitation methodology.