Electrocatalytic Oxidation of 5-(Hydroxymethyl)furfural Using High-Surface-Area Nickel Boride

Stefan Barwe; Jonas Weidner; Steffen Cychy; Dulce M Morales; Stefan Dieckhöfer; Dennis Hiltrop; Justus Masa; Martin Muhler; Wolfgang Schuhmann

doi:10.1002/anie.201806298

Electrocatalytic Oxidation of 5-(Hydroxymethyl)furfural Using High-Surface-Area Nickel Boride

Angew Chem Int Ed Engl. 2018 Aug 27;57(35):11460-11464. doi: 10.1002/anie.201806298. Epub 2018 Jul 31.

Authors

Stefan Barwe¹, Jonas Weidner¹, Steffen Cychy², Dulce M Morales¹, Stefan Dieckhöfer¹, Dennis Hiltrop², Justus Masa¹, Martin Muhler², Wolfgang Schuhmann¹

Affiliations

¹ Analytical Chemistry-Center for Electrochemical Sciences (CES), Faculty of Chemistry and Biochemistry, Ruhr-Universität Bochum, Universitätsstraße 150, 44780, Bochum, Germany.
² Laboratory of Industrial Chemistry, Faculty of Chemistry and Biochemistry, Ruhr-Universität Bochum, Universitätsstraße 150, 44780, Bochum, Germany.

PMID: 29985550
DOI: 10.1002/anie.201806298

Abstract

The electrochemical oxidation of the biorefinery product 5-(hydroxymethyl)furfural (HMF) to 2,5-furandicarboxylic acid (FDCA), an important platform chemical for the polymer industry, is receiving increasing interest. FDCA-based polymers such as polyethylene 2,5-furandicarboxylate (PEF) are sustainable candidates for replacing polyethylene terephthalate (PET). Herein, we report the highly efficient electrocatalytic oxidation of HMF to FDCA, using Ni foam modified with high-surface-area nickel boride (Ni_x B) as the electrode. Constant potential electrolysis in combination with HPLC revealed a high faradaic efficiency of close to 100 % towards the production of FDCA with a yield of 98.5 %. Operando electrochemistry coupled to ATR-IR spectroscopy indicated that HMF is oxidized preferentially via 5-hydroxymethyl-2-furancarboxylic acid rather than via 2,5-diformylfuran, which is in agreement with HPLC results. This study not only reports a low-cost active electrocatalyst material for the electrochemical oxidation of HMF to FDCA, but additionally provides insight into the reaction pathway.

Keywords: ATR-IR; HMF oxidation; electrocatalysis; electrosynthesis; nickel boride.