5-Hydroxymethylfurfural Oxidation to 2,5-Furandicarboxylic Acid on Noble Metal-Free Nanocrystalline Mixed Oxide Catalysts

Noble metal-free catalysts based on earth-abundant and inexpensive mixed oxides are active catalysts of all steps of the reaction cascade leading from 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) using tert-butyl hydroperoxide (TBHP) as oxidation agent. Catalysts covering the whole range of composition in the Cu-Mn and Co-Fe series have been prepared and characterised. The nature and composition of the catalyst strongly affect conversion and selectivity. The distribution of products indicates that radical-type oxygen species, deriving from the activation of TBHP, play a determining role in the reaction. The early steps of reaction mainly follow the pattern expected for heterogeneous Fenton catalysts. Mixed oxide catalysts are the most effective in further oxidation steps, leading to the formation of FDCA, both in the Cu-Mn and Co-Fe systems. This behaviour can be related to the distribution of charge in the mixed oxides, suggesting a possible implication of the lattice oxygen in the last reaction steps. The results provide indications on how to optimize the reaction and minimize the formation of byproducts (humins and oligomers)