Engineering a homogeneous alloy-oxide interface derived from metal-organic frameworks for selective oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid

[Display omitted] •ZIF-derived, Au-Pd alloy nanoparticles-doped cobalt oxide (AuPd@Co3O4) is synthesized for the first time.•The AuPd@Co3O4 sample shows uniform distribution of Au and Pd inside ZIF-derived Co3O4.•The AuPd@Co3O4 catalyst exhibits superior activity for 5-hydroxymethylfurfural (HMF) oxidation into 2,5-furandicarboxylic acid (FDCA).•Engineering the homogeneous interface between Au-Pd alloy and Co3O4 is studied with XPS and XANEF.•Mechanism and kinetics of HMF-to-FDCA conversion is comprehensively investigated. The selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is an important biomass conversion reaction. However, the multiple intermediates of the reaction make the catalyst design challenging. We engineered an active and selective catalyst with an active interface between Au-Pd alloy nanoparticles (NPs) and cobalt oxide supports via calcination of a composite of NPs encapsulated in metal-organic frameworks (MOFs). The catalyst shows an effective HMF-to-FDCA oxidation with total conversion and 95 % yield by 10 % hydrogen peroxide solution at 90 °C in one hour under atmospheric pressure. The mechanistic study shows that the engineered interface promotes the formation of hydroperoxyl radicals and dioxygen molecules, which accelerate the oxidation of reactive intermediates to FDCA. This work demonstrates the advantage of using MOF composites as a precursor to generate complex but active interfaces with a strong interaction between the metal and metal oxides.