From cellulose to FDCA: catalytic strategies, mechanisms, and process design for converting cellulose into 5-hydroxymethylfurfural and 2,5-furandicarboxylic acid
摘要
The conversion of renewable biomass into value-added platform chemicals is critical for sustainable chemical production. 5-Hydroxymethylfurfural (5-HMF), a pivotal intermediate derived from cellulose, holds enormous potential as a bio-based precursor for fuels, polymers, and fine chemicals. This review critically surveys developments (2020–2025) in the tandem valorization of cellulose to 5-hydroxymethylfurfural (5-HMF) and the subsequent oxidation of 5-HMF to 2,5-furandicarboxylic acid (FDCA). We synthesize recent advances in heterogeneous and homogeneous catalysis, solvent engineering, electro- and photocatalytic approaches, and reactor concepts that enable efficient depolymerization, isomerization and dehydration (cellulose → glucose → fructose → 5-HMF) and aerobic/electrochemical/photocatalytic oxidation pathways. For the cellulose → 5-HMF stage we analyze solid bifunctional catalysts, ionic liquids and deep eutectic solvents (DESs), biphasic extraction systems, and mechanical/chemical pretreatments. Reported 5-HMF yields span broadly, with high selectivity achieved using tailored acid-site ratios, hydrophobicity tuning, solvent partitioning and continuous extraction. For 5-HMF → FDCA, we review aerobic heterogeneous oxidation, electrocatalytic oxidation, photocatalysis, and combined enzymatic–nanozyme cascades. Electrochemical routes report high Faradaic efficiencies and scale demonstrations, while heterogeneous aerobic catalysts achieve high FDCA selectivities under base-free conditions by engineering oxygen activation, oxygen vacancies, and alloying. We highlight mechanistic insights: the essential role of balanced Brønsted/Lewis acidity for glucose isomerization and fructose dehydration, solvent and salt effects on rate-limiting steps, the importance of removing 5-HMF from aqueous phase to limit humin formation, the rate-determining FFCA→FDCA step in many aerobic systems, and how electrode surface reconstruction governs electrocatalytic performance. Finally, we assess catalyst stability, recycling, process intensification, and techno-operational trade-offs between activity, selectivity and durability. The review concludes with targeted research directions to bridge laboratory advances with pilot and industrial deployment of biomass-to-FDCA value chains.