Selective aerobic oxidation of 5-HMF into 2,5-furandicarboxylic acid with Pt catalysts supported on TiO2 - and ZrO2 -based supports

Abstract

Pt catalysts prepared over different metallic oxide supports were investigated in the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) in alkaline aqueous solutions with air, to examine the combined effect of the support and base addition. The base (nature and amount) played a significant role in the degradation or oxidation of HMF. Increasing amounts of the weak NaHCO3 base improved significantly the overall catalytic activity of Pt/TiO2 and Pt/ZrO2 by accelerating the oxidation steps, especially for the aldehyde group. This was highlighted by a proposed kinetic model that gave very good concentration-time fittings. Moreover, the promotion of the catalyst with bismuth yielded a PtBi/TiO2 catalytic system with improved activity and stability. Y2 O3  and La2 O3 ZrO2 -supported catalysts exhibited lower activity than Pt/ZrO2 , which suggests no cooperative effect of the weakly basic properties introduced and the homogeneous base. Quantitative oxidation of HMF (0.1 M) and high yields of FDCA (>99 %) were obtained in less than 5 h by using an HMF/Pt molar ratio of 100 and Na2 CO3 as a weak base over PtBi/TiO2 (Bi/Pt=0.22).

Keywords: biomass; bismuth; oxidation; platinum; supported catalysts.