Abstract This study investigated the performance of a novel integrated bio-electrochemical system for synergistic hydrogen production from a process combining a dark fermentation reactor and a galvanic cell. The operating principle of the system is based on the electrochemical conversion of protons released upon dissociation of the acid metabolites of the biological process and is mediated by the electron flow from the galvanic cell, coupling biochemical and electrochemical hydrogen production. Accordingly, the galvanic compartment also generates electricity. Four different experimental setups were designed to provide a preliminary assessment of the integrated bio-electrochemical process and identify the optimal configuration for further tests. Subsequently, dark fermentation of cheese whey was implemented both in a stand-alone biochemical reactor and in the integrated bio-electrochemical process. The integrated system achieved a hydrogen yield in the range 75.5–78.8?N?LH2/kg?TOC, showing a 3 times improvement over the biochemical process.Graphical abstract
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