tert-Butyl hydroperoxide-mediated rapid 30-second oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid

Abstract

The selective conversion of 5-hydroxymethylfurfural (5-HMF) into 2,5-furandicarboxylic acid (FDCA) remains a significant challenge in biomass valorization. Traditional oxidation methods relying on O₂ or H₂O₂ suffer from inherent limitations. Herein, we developed a novel Au/CeO₂-catalyzed system using tert-butyl hydroperoxide (TBHP) in aqueous media that achieved 95% FDCA selectivity at full conversion within 30 s at 90 °C. Optimization of base concentration enabled precise control over both reaction kinetics and catalyst durability. Mechanistic investigations revealed two synergistic effects: (1) TBHP-derived radicals exhibited prolonged stability for efficient electron scavenging and (2) van der Waals interactions between TBHP's tert-butyl group and HMF's furan ring promoted spatial proximity, thereby accelerating oxidative activation.