Paired Electrolysis of Acrylonitrile and 5-Hydroxymethylfurfural for Simultaneous Generation of Adiponitrile and 2,5-Furandicarboxylic Acid

The classic acrylonitrile (AN) electrohydrodimerization (EHD) to adiponitrile (ADN) process produces oxygen on the anode side. The oxygen evolution reaction (OER) is energy consuming, and O2is of low value and has security issues while directly contacting with organic molecules. Herein, by replacing OER with 5-hydroxymethylfurfural oxidation reaction (HMFOR), we report paired electrolysis of AN and HMF for simultaneous generation of ADN and 2,5-furandicarboxylic acid (FDCA). On the anode side, the electrodeposited amorphous NiMoP film-covered nickel foam efficiently boosted HMFOR activity by enlarging the electrochemically active surface area (ECSA) via in situ selective removal of Mo and P on the surface. On the cathode side, addition of dimethylformamide (DMF) as a cosolvent enhanced the reaction efficiency of ANEHD by forming a single-phase electrolyte that offers better interaction between AN and the electrode. The ANEHD–HMFOR paired system shows excellent generation rates of FDCA (0.018 gFDCA·h−1·cm−2) and ADN (0.017 gADN·h−1·cm−2) at a high cell current (160 mA). An amount of 1 kWh of electricity can produce 2.91 mol of ADN and 0.53 mol of FDCA with 107.1% Faraday efficiency.Keywords:paired electrolysis;5-hydroxymethylfurfural oxidation;acrylonitrile electrohydrodimerization;adiponitrile;2,5-furandicarboxylic acid;dimethylformamide cosolvent