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

Li, Wenzhen
Liu, Hengzhou
Lee, Ting-Han
Chen, Yifu
Cochran, Eric
Cochran, Eric
Li, Wenzhen
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Chemical and Biological Engineering

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


This is the peer-reviewed version of the following article: Liu, Hengzhou, Ting-Han Lee, Yifu Chen, Eric Cochran, and Wenzhen Li. "Paired and Tandem Electrochemical Conversion of 5‐(Hydroxymethyl) furfural Using Membrane‐Electrode Assembly‐Based Electrolytic Systems." ChemElectroChem (2021) which has been published in final form at DOI: 10.1002/celc.202100662. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. Posted with permission.