An Anderson-type polyoxometalate triggers aerobic oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran

Aerobic oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) is an environmentally sustainable, economically feasible, but substantially challenging conversion owing to the high energy barrier of O2 activation. Herein, we report a catalyst with Mo5+ connected to the oxygen vacancies (Mo5+) in Anderson-type polyoxometalate (POM) [(C18H37)2N(CH3)2]6Mo7O24 for oxidizing HMF to DFF. The resultant catalyst with high Mo5+ content presents superior HMF oxidation performance, delivering a > 99% DFF selectivity with complete HMF conversion. Mechanistic studies and density functional theory (DFT) calculations reveal that the Mo5+- species in the catalyst facilitate O2 activation and HMF oxidation. Moreover, the catalyst exhibits outstanding catalytic stability during the aerobic oxidation of HMF to DFF.

Automated summary

In this study, a catalyst with Mo5+ connected to the oxygen vacancies in Anderson-type polyoxometalate was developed for the oxidation of HMF to DFF. The catalyst exhibited excellent oxidation performance, high selectivity, and remarkable stability.