Oxidative Esterification of 5-Hydroxymethylfurfural into Dimethyl 2,5-Furandicarboxylate Using Gamma Alumina-Supported Gold Nanoparticles.

Gold nanoparticles (Au NPs) supported on a nanostructured gamma alumina (γ-AlO) fiber can exhibit excellent catalytic activity for the conversion of 5-hydroxymethylfurfural to produce its ester derivative, dimethyl 2,5-furandicarboxylate (FDMC). γ-AlO was synthesized using a PEG surfactant to generate oxide fibers that randomly stack together into irregular shapes. The average particle sizes of the Au NPs are 1-6 nm, where the catalytically active Au (111) surface is the exposed facet. This 3D nanocatalyst architecture enhances the 5-hydroxymethylfurfural (HMF) oxidative esterification because HMF reactant molecules can readily diffuse into this fibrous structure and adsorb to active catalytic sites, while ester product molecules can diffuse out. Up to 99% HMF conversion and 90% FDMC selectivity can be obtained at a low reaction temperature of 45 °C, and the catalyst shows excellent recyclability. Increasing the Au content in the catalyst minimizes the requirement of a base for HMF conversion. Thus, the Au NPs supported on γ-AlO can drive HMF esterification to FDMC efficiently with high product selectivity under very mild reaction conditions, omitting the need for an additional esterification step of the HMF acid.