Direct synthesis of hydrogen peroxide and benzyl alcohol oxidation using Au-Pd catalysts prepared by sol immobilization.

We report the preparation of Au-Pd nanocrystalline catalysts supported on activated carbon prepared via a sol-immobilization technique and explore their use for the direct synthesis of hydrogen peroxide and the oxidation of benzyl alcohol. In particular, we examine the synthesis of a systematic set of Au-Pd colloidal nanoparticles having a range of Au/Pd ratios. The catalysts have been structurally characterized using a combination of UV-visible spectroscopy, transmission electron microscopy, STEM HAADF/XEDS, and X-ray photoelectron spectroscopy. The Au-Pd nanoparticles are found in the majority of cases to be homogeneous alloys, although some variation is observed in the AuPd composition at high Pd/Au ratios. The optimum performance for the synthesis of hydrogen peroxide is observed for a catalyst having a Au/Pd 1:2 molar ratio. However, the competing hydrogenation reaction of hydrogen peroxide increases with increasing Pd content, although Pd alone is less effective than when Au is also present. Investigation of the oxidation of benzyl alcohol using these materials also shows that the optimum selective oxidation to the aldehyde occurs for the Au/Pd 1:2 molar ratio catalyst. These measured activity trends are discussed in terms of the structure and composition of the supported Au-Pd nanoparticles.

Oxidation of glycerol using gold-palladium alloy-supported nanocrystals.

The use of bio-renewable resources for the generation of materials and chemicals continues to attract significant research attention. Glycerol, a by-product from biodiesel manufacture, is a highly functionalised renewable raw material, and in this paper the oxidation of glycerol in the presence of base using supported gold, palladium and gold-palladium alloys is described and discussed. Two supports, TiO(2) and carbon, and two preparation methods, wet impregnation and sol-immobilisation, are compared and contrasted. For the monometallic catalysts prepared by impregnation similar activities are observed for Au and Pd, but the carbon-supported monometallic catalysts are more active than those on TiO(2). Glycerate is the major product and lesser amounts of tartronate, glycolate, oxalate and formate are observed, suggesting a sequential oxidation pathway. Combining the gold and palladium as supported alloy nanocrystals leads to a significant enhancement in catalyst activity and the TiO(2)-supported catalysts are significantly more active for the impregnated catalysts. The use of a sol-immobilisation preparation method as compared to impregnation leads to the highest activity alloy catalysts and the origins of these activity trends are discussed.