Oxidation of glycerol using supported Pt, Pd and Au catalysts

Abstract

The oxidation of aqueous solutions of glycerol is described and discussed for Pd, Pt and Au nanoparticles supported on graphite and activated carbon. The oxidation in a batch reactor at 60 °C and 1 bar pressure using air as oxidant was initially investigated. Under these conditions, supported Pd and Pt catalysts give some selectivity to glyceric acid, but the main reaction products are considered to be non-desired C₁ by-products, e.g. CO₂, HCHO and HCOOH. In addition, under these conditions, supported Au catalysts were totally inactive. Using an autoclave with pure oxygen at 3 bar pressure gave a significant improvement in reactivity and, for Pt and Au catalysts, the formation of C₁ by-products was eliminated when NaOH was added. In particular, it was noted that, in the absence of NaOH, the Au/C catalyst was inactive. For 1 wt.% Au/graphite or activated carbon, 100% selectivity to glyceric acid at high conversion was readily achieved. The role of the base is discussed and it is proposed that the base aids the initial dehydrogenation via H-abstraction of one of the primary OH groups of glycerol and, in this way, the rate limiting step in the oxidation process is overcome.