Improved electrosynthesis of biomass derived furanic compounds via redox mediation design Emily Carroll , Shelley Minteer University of Utah, USA Global industrialization has escalated the demand for energy while contributing to carbon emissions, global warming, and climate change. To avoid irreparable damage to the atmosphere and ecosystems on earth, there is an increasing urgency for renewable energy, electrofuels, and fine chemical production derived independently from fossil fuel resources (e.g., coal, crude oil, natural gas). Sustainable resources such as biomass have shown promise as a versatile and renewable feedstock and an alternative source for chemicals and energy derived from petroleum ( 1 ). Biomass refers to plant matter such as grasses, woods, and crop residues (corn stover, wheat straw, sugar cane), and it is the most abundantly available raw material for the production of biofuels (annual production of biomass exceeding 170 billion tons) ( 2 ). Several important transformations stem from the biomass-derived furan molecule 5-hydroxymethylfurfural (HMF) and its derivatives ( 1,3 ). A key transformation of HMF is oxidation into the high value-added product 2,5-furan dicarboxylic acid (FDCA). FDCA is a precursor for polymeric materials including polyethylene furandicarboxylate (PEF), a bio-based alternative to petroleum- derived polyethylene terephthalate (PET) ( 4 ). However, traditional methods for the catalytic conversion of furan molecules rely on noble metal catalysts, organic solvents, and high temperatures and pressures. Alternatively, electrochemistry offers a streamlined approach to the synthesis of furan derivatives by eliminating the need for extensive oxidizing reagents and harsh reaction conditions. Instead, an applied electric potential serves as thermodynamic driving force for catalysis at lower temperatures. Here, we explore the electrochemical transformation of a reduced furan derivative, 2,5-bis(hydroxymethyl)furan (BHMF) to the polymeric precursor FDCA via mediated electrocatalysis. Not only has mediated electrochemical oxidation yet to be demonstrated for BHMF transformations, but this reaction also has the merit of running in aqueous conditions. Utilizing a library of redox mediators, we identify the key molecular parameters necessary for catalyzing selective alcohol oxidation. Using both transient techniques (cyclic voltammetry) to study mechanism and preparative scale electrolysis to study selectivity, we aim to build a comprehensive and predictive picture of mediated furan transformations, an under-utilized strategy in the present literature. These studies represent an opportunity for advancement in commodity chemical production from biomass. References 1. Simoska, O.; Rhodes, Z.; Weliwatte, S.; Cabrera-Pardo, J. R.; Gaffney, E. M.; Lim, K.; Minteer, S. D. Advances in Electrochemical Modification Strategies of 5-Hydroxymethylfurfural. ChemSusChem 2021, 14 (7), 1674-1686. 2. Röper, H. Renewable Raw Materials in Europe- Industrial Utilisation of Starch and Sugar. Starch - Stärke 2002, 54 (3-4), 89-99. 3. Zakrzewska, M. E.; Bogel-Łukasik, E.; Bogel-Łukasik, R. Ionic Liquid-Mediated Formation of 5-Hydroxymethylfurfural—A Promising Biomass-Derived Building Block. Chemical Reviews 2011, 111 (2), 397-417. 4. Marshall, A.; Jiang, B.; Gauvin, R. M.; Thomas, C. M. 2,5-Furandicarboxylic Acid: An Intriguing Precursor for Monomer and Polymer Synthesis. In Molecules, 2022; Vol. 27.
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