Sustainable production of 2,5-diformylfuran via peroxymonosulfate-triggered mild catalytic oxidation of lignocellulosic biomass

PNAS Nexus. 2024 Dec 17;4(1):pgae563. doi: 10.1093/pnasnexus/pgae563. eCollection 2025 Jan.

Abstract

The relentless depletion of fossil fuels accentuates the urgent necessity for the sustainable synthesis of chemicals from renewable biomass. 5-Hydroxymethylfurfural (HMF), extracted from lignocellulosic biomass, emerges as a beacon of hope for conversion into value-added chemicals. However, the inherent susceptibility of its unsaturated aldehyde groups to excessive oxidation often culminates in undesired reactions, compromising both the yield and specificity of the desired products. Here, we introduce a holistic methodology for the cost-effective and ecologically responsible generation of 2,5-diformylfuran (DFF), through the heterogeneously catalyzed oxidation of HMF utilizing peroxymonosulfate (PMS) under benign conditions. This strategy, characterized by the meticulous enhancement of surface ketone groups via a mixed-salt-assisted co-pyrolysis technique, achieves an unparalleled selective activation of PMS, engendering singlet oxygen to catalyze the oxidation of HMF into DFF with a selectivity surpassing 80%. Life-cycle assessments underscore a negligible impact on human health, ecosystems, and natural resources, endorsing the holistic utilization of biomass. This integration of pyrolysis for the creation of functional carbonaceous materials within biomass conversion processes significantly enhances sustainability and economic viability, while paving green pathways for selective biomass oxidation and the production of high-value chemicals.

Keywords: 2,5-diformylfuran; biomass upgrading; ketone; selective oxidation; singlet oxygen.