Improved Electrosynthesis of Biomass Derived Furanic Compounds via Nitroxyl Radical Redox Mediation

Biomass is an abundantly available, underutilized feedstock for the production of bulk and fine chemicals, polymers, and sustainable and biodegradable plastics that are traditionally sourced from petrochemicals. Among potential feedstocks, 2,5-furan dicarboxylic acid (FDCA) stands out for its potential to be converted to higher-value polymeric materials such as polyethylene furandicarboxylate (PEF), a bio-based plastic alternative. In this study, the sustainable, electrocatalytic oxidation of stable furan molecule 2,5-bis(hydroxymethyl)furan (BHMF) to FDCA is investigated using a variety of TEMPO derivative electrocatalysts in a mediated electrosynthetic reaction. Three TEMPO catalysts (acetamido-TEMPO, methoxy-TEMPO, and TEMPO) facilitate full conversion to FDCA in basic conditions with >90% yield and >100% Faradaic efficiency. The remaining three TEMPO catalysts (hydroxy-TEMPO, oxo-TEMPO, and amino-TEMPO) all perform intermediate oxidation of BHMF in basic conditions but do not facilitate full conversion to FDCA. On the basis of pH studies completed on all TEMPO derivatives to assess their electrochemical reversibility and response to substrate, pH and reversibility play significant roles in the catalytic ability of each catalyst, which directly influences catalyst turnover and product formation. More broadly, this study also highlights the importance of an effective and rapid electroanalytical workflow in mediated electrosynthetic reactions, demonstrating how voltammetric catalyst screening can serve as a useful tool for predicting the reactivity and efficacy of a catalyst–substrate electrochemical system.