Paired and Tandem Electrochemical Conversion of 5‐(Hydroxymethyl)furfural Using Membrane‐Electrode Assembly‐Based Electrolytic Systems

Pairing the electrocatalytic hydrogenation (ECH) reaction with different anodic reactions holds great promise for producing value-added chemicals driven by renewable energy sources. Replacing sluggish water oxidation a bio-based upgrading can reduce overall cost and allows simultaneous generation of high-value products at both electrodes. Herein, we developed membrane-electrode assembly (MEA)-based electrolysis system conversion 5-(hydroxymethyl)furfural (HMF) to bis(hydroxymethyl)furan (BHMF) 2,5-furandicarboxylic acid (FDCA). With (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO)-mediated electrochemical (ECO) HMF anode, unique zero-gap configuration enabled minimal cell voltage 1.5 V 10 mA, which was stable during 24-hour period continuous electrolysis, resulting in combined faradaic efficiency (FE) as high 139 % BHMF FDCA. High FE also obtained pH-asymmetric mediator-free configuration, ECO carried out 0.1 M KOH an electrodeposited NiFe oxide catalyst bipolar membrane. Taking advantage low resistance MEA-based system, explored ECH current density (280 mA cm−2), 24 towards achieved. The co-generated H2 supplied into batch reactor tandem catalytic furfural or benzaldehyde under ambient conditions, additional 7.3 indirect single-pass operation. co-electrolysis bio-derived molecules electrocatalytic-catalytic process provide sustainable avenues distributed, flexible, energy-efficient routes synthesis valuable chemicals.