Enhancing bioelectrochemical hydrogen production from industrial wastewater using Ni-foam cathodes in a microbial electrolysis cell pilot plant

Microbial electrolysis cells (MECs) have garnered significant attention as a promising solution for industrial wastewater treatment, enabling the simultaneous degradation of organic compounds and biohydrogen production. Developing efficient and cost-effective cathodes to drive the hydrogen evolution reaction is central to the success of MECs as a sustainable technology. While numerous lab-scale experiments have been conducted to investigate different cathode materials, the transition to pilot-scale applications remains limited, leaving the actual performance of these scaled-up cathodes largely unknown. In this study, nickel-foam and stainless-steel wool cathodes were employed as catalysts to critically assess hydrogen production in a 150 L MEC pilot plant treating sugar-based industrial wastewater. Continuous hydrogen production was achieved in the reactor for more than 80 days, with a maximum COD removal efficiency of 40 %. Nickel-foam cathodes significantly enhanced hydrogen production and energy efficiency at non-limiting substrate concentration, yielding the maximum hydrogen production ever reported at pilot-scale (19.07 ± 0.46 L H₂ m⁻² d⁻¹ and 0.21 ± 0.01 m³ m⁻³ d⁻¹). This is a 3.0-fold improve in hydrogen production compared to the previous stainless-steel wool cathode. On the other hand, the higher price of Ni-foam compared to stainless-steel should also be considered, which may constrain its use in real applications. By carefully analysing the energy balance of the system, this study demonstrates that MECs have the potential to be net energy producers, in addition to effectively oxidize organic matter in wastewater. While higher applied potentials led to increased energy requirements, they also resulted in enhanced hydrogen production. For our system, a conservative applied potential range from 0.9 to 1.0 V was found to be optimal. Finally, the microbial community established on the anode was found to be a syntrophic consortium of exoelectrogenic and fermentative bacteria, predominantly Geobacter and Bacteroides, which appeared to be well-suited to transform complex organic matter into hydrogen.