We present the Keggin-type polyoxometalate H6[PV3Mo9O40] as a switchable catalyst being able to catalyze the transformation of both glucose and glyceraldehyde to formic acid (42%) and lactic acid (40%), respectively, within 1 h reaction time by simply changing the reaction atmosphere at 160 °C from oxygen to nitrogen in one reactor setup. In detail, we report the influence of different gas atmospheres and reaction temperatures on various vanadium-containing catalysts in the selective transformation of several biogenic substrates to carboxylic acids with a special emphasis on reaction pathways and switchability of the catalyst systems. All investigations were carried out in parallel using either an oxygen or a nitrogen atmosphere of 20 bar performing time-resolved experiments between 0.25 and 5 h and a temperature variation from 160 to 200 °C. Furthermore, a catalyst and a substrate variation led to the reaction system consisting of glyceraldehyde and the Keggin-type polyoxometalates (POM) H6[PV3Mo9O40] as the best switchable reaction system under the applied conditions. This study shows interesting potential for using both Keggin-type and Lindqvist-type POMs as switchable catalysts for selective biomass conversion to platform chemicals.
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