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Electrochemical Biomass Upgrading of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid Under Mild Alkaline Media
Summary
Researchers developed an electrochemical method to upgrade biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) under mild alkaline conditions, positioning FDCA as a bio-based monomer for producing poly(ethylene furoate) as a green alternative to petroleum-derived plastics. The study demonstrated that electrochemical oxidation under mild conditions offers a viable, lower-emission route to sustainable plastic precursors from renewable biomass feedstocks.
Biomass holds promise as a substitute for carbon sources derived from fossil fuels, which are known for their production of CO 2 emissions and contribution to microplastic pollution. 2,5-Furandicarboxylic acid (FDCA) from biomass-derived 5-hydroxymethylfurfural (HMF) has emerged as a green plastic because it is a monomer of poly(ethylene furoate), poised as a viable alternative to poly(ethylene terephthalate) due to its robust mechanical properties and environmentally sustainable production. An electrochemical oxidation reaction of HMF to FDCA (HMFOR) has been studied actively due to the high performance and cost-effectiveness of transition metal catalysts. Furthermore, it demonstrates a lower overpotential for water splitting by substituting the anodic reaction from oxygen evolution reaction (OER) to HMFOR with value-added FDCA production than oxygen. The majority of HMFOR research has been carried out in highly alkaline media (1 M KOH) because the OH - serves as a reactant and accelerates the HMFOR. Nevertheless, this approach is not conducive to scaling up concentrated HMFOR processes due to the risk of high OH - concentrations, which leads to the instability of HMF through polymerization into humin. Herein, we investigate the HMFOR under mild alkaline media, ensuring the preservation of HMF, facilitated by a Cu-Ni based catalyst. In contrast to the conditions at high pH, the oxidation of aldehyde groups was inhibited due to the lack of sufficient OH - , which hindered the OH - mediated formation of germinal diols. Through several in situ studies, we proposed that Cu induces the adsorption of OH - and HMF, promoting the geminal diol formation, and Ni acts as the most active site of HMFOR. This research would be expected to provide strategies for achieving highly efficient HMFOR while maintaining the stability of HMF via suppression of the OH - mediated humin polymerization.
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