Selective electrocatalytic hydrogenation of lignocellulose-derived 5-hydroxymethylfurfural with superior productivities

Recently, valorization of biomass to value-added chemicals has drawn increasing attention due to carbon neutrality and sustainability. 5-Hydroxymethylfurfural is an important lignocellulose-derived biomass molecule. Herein, we have demonstrated the efficient electrocatalytic hydrogenation of 5-hydroxymethylfurfural to value-added 2,5-bis(hydroxymethyl)furan. An optimized electrolyzer with a highly electrolyte-permeable Pd cathode well balanced the selectivity, faradaic efficiency, and productivity. We have achieved high selectivity (97%) and faradaic efficiency (72%) at 50 mA cm-2 current density, and a record high productivity of 0.923 mmol cm-2·h-1 at 100 mA cm-2 current density, ∼2 times advanced compared with the best productivity in prior reports. We applied in situ infrared reflection-absorption spectroscopy to investigate the electrode-potential-dependent reaction pathways and mechanism, confirming that the highly selective hydrogenation of HMF is due to the tilted adsorption geometry through carbonyl group bonding to the surface of electrode. This work offers an opportunity for the sustainable electrocatalytic valorization of renewable lignocellulose-derived biomass with superior productivities approaching industrial level.