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This study elucidates the mechanism enabling the low-voltage electrolysis of black liquor (BL) for integrated resource recovery. The process simultaneously generates protons at the anode via the oxidation of organics (OOR), which occurs at a lower potential than the oxygen evolution reaction (OER), and induces lignin precipitation. Concurrently, hydrogen and hydroxide ions are produced at the cathode through the hydrogen evolution reaction (HER). Driven by the electric field, sodium ions migrate from the anode to the cathode chamber, combining with hydroxide ions to form sodium hydroxide, thereby achieving the synchronous production of acid, alkali, hydrogen, and modified lignin in a single process. Using a platinum electrode, we conducted a mechanistic investigation through linear sweep voltammetry (LSV), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and detailed product analysis. The results show that overall efficiency is controlled by competition at the anode between OOR and OER, which directly determines proton yield. A critical trade-off exists between anodic proton generation and cathodic alkali recovery, driven by the competitive migration of protons and sodium ions across the cation-exchange membrane. The proton yield was highly dependent on the initial BL composition, with a characteristic peak observed under specific conditions. Conversely, the sodium hydroxide recovery rate was maximized when the anolyte pH remained high, minimizing competitive proton migration. This work provides fundamental insights into the interfacial mechanisms of BL electrocatalytic, establishing it as a versatile electrochemical biorefinery platform for simultaneous proton and alkali production from a renewable waste stream, beyond its role as a hydrogen source and lignin recovery.