Electro-Reforming of Biomass Gasification Tar with Simultaneous Hydrogen Evolution

In this study, an electrochemical valorization strategy on liquid byproducts from hazelnut shell gasification was developed to couple waste remediation with energy-efficient hydrogen production. The aqueous phase, rich in organic compounds, is processed in an anion exchange membrane (AEM) cell, where pure hydrogen evolved at the cathode while organic pollutants are oxidized at the anode. First, the feedstock is thoroughly characterized using gas chromatography–mass spectrometry (GC-MS), identifying a complex matrix of water-soluble aromatic compounds such as phenols, catechols, and other aromatics compounds, with concentrations reaching up to 2.9 g/kg for catechols. Then, the electro-reforming process is optimized using Nickel oxide–hydroxide (Ni(O)OH) electrodes with a loading of 0.75 mg/cm2. This methodology relies on the favorable thermodynamics of organic oxidation, which requires a lower onset potential (0.4 V) compared to the oxygen evolution reaction (OER) observed in the alkaline control (0.52 V), and the low overpotential of the Nickel oxide–hydroxide electrode towards the oxidized species. Consequently, the organic load undergoes progressive oxidation into hydrophilic and less bioaccumulating species and carbon dioxide, allowing for the simultaneous generation of pure hydrogen at the cathode at a reduced cell voltage. Elevated stability was observed, with a substantial abatement—78% of the initial organic load—of organic compounds achieved over 80 h at a fixed cell voltage of 0.5 V, and a specific energy consumption for hydrogen production of 38.5 MJ⋅kgH2−1. This represents a step forward in the development of technologies that reduce the energy intensity of hydrogen generation while valorizing biomass gasification residues.