Organic Oxidation-assisted Hydrogen Production: Glycerol Electroreforming to Formate on Nickel Diselenide Nanoparticles

The energy efficiency of water electrolysis is limited by the sluggish kinetics of the anodic oxygen evolution reaction (OER), which simultaneously produces a low-value product, oxygen. A promising strategy to address this challenge is to replace OER with a more favorable oxidation reaction that yields a valuable co-product. In this study, we investigate the electrochemical reforming of glycerol in alkaline media to simultaneously produce hydrogen at a Pt cathode and formate at a NiSe₂ anode. The NiSe₂ electrode achieves a glycerol oxidation reaction (GOR) current density of up to 100 mA cm−2 in a 1 M KOH solution containing 1 M glycerol, significantly outperforming a reference elemental Ni electrode. Both electrodes exhibit high Faradaic efficiencies (FE), achieving around 93 % for formate production at an applied potential of 1.6 V vs. RHE. To rationalize this exceptional performance, density functional theory (DFT) calculations were conducted, revealing that the incorporation of Se into NiSe₂ enhances the glycerol adsorption and modulates the electron density, thereby lowering the energy barrier for the initial dehydrogenation step in the formate formation pathway. These findings provide valuable insights for the design of cost-effective, high-performance electrocatalysts for organic oxidation-assisted hydrogen production, advancing a more sustainable and economically attractive route for hydrogen generation and chemical valorization.