Optimization of 5-hydroxymethylfurfural oxidation via photo-enzymatic cascade process

This study investigated the oxidation of 5-hydroxymethylfurfural (HMF) to produce valuable products such as 2,5-furandicarboxaldehyde (DFF), 5-formyl-2-furancarboxylic acid (FFCA) and 2,5-furandicarboxylic acid (FDCA) through (photo) chemical and enzymatic catalysis. Laccases from different sources, including Aspergillus spp., Pseudomonas cepacea, and Trametes versicolor, were evaluated for their catalytic activity in the HMF oxidation. Laccase from Trametes versicolor (LacTV) emerged as the most effective catalyst, achieving complete conversion of HMF under specific pH conditions. The reaction mechanisms were explored, revealing a preference for the primary alcohol oxidation pathway over the aldehyde, leading to the formation of DFF and subsequent conversion to FFCA and FDCA. The impact of substrate concentration on HMF conversion was examined, revealing optimal conversion at lower HMF concentrations (<100 mM) and reduced performance at higher concentrations (>100 mM). The study also examined the influence of blue light (430 nm) on this reaction, revealing the dependence on light exposure for gC(3)N(4) based catalysts and a negative effect for LacTV. Furthermore, the study introduces a modular flow chemical platform that utilizes Continuous Stirred Tank Reactors (CSTR) in a cascade configuration, the optimization of HMF oxidation. The implementation of this innovative approach has led to the effective synthesis of FDCA, demonstrating an impressive 40-fold increase in productivity compared to the traditional batch system. These results present significant potential for advancing green chemistry and sustainable chemical synthesis, introducing novel possibilities for environmentally friendly HMF oxidation processes.