Combining autoclave and LCWM reactor studies to shed light on the kinetics of glucose oxidation catalyzed by doped molybdenum-based heteropoly acids

Abstract

In this work we combined kinetic studies for aqueous-phase glucose oxidation in a high-pressure autoclave setup with catalyst reoxidation studies in a liquid-core waveguide membrane reactor. Hereby, we investigated the influence of Nb- and Ta-doping on Mo-based Keggin-polyoxometalates for both reaction steps independently. Most importantly, we could demonstrate a significant increase of glucose oxidation kinetics by Ta- and especially Nb-doping by factors of 1.1 and 1.5 compared to the classical HPA-Mo. Moreover, activation energies for the substrate oxidation step could be significantly reduced from around 80 kJ mol⁻¹ for the classical HPA-Mo to 61 kJ mol⁻¹ for the Ta- and 55 kJ mol⁻¹ for the Nb-doped species, respectively. Regarding catalyst reoxidation kinetics, the doping did not show significant differences between the different catalysts.