A study of electron source preference and its impact on hydrogen production in microbial electrolysis cells fed with synthetic fermentation effluent

Fermentation effluents from organic wastes contain simple organic acids and ethanol, which are good electron sources for exoelectrogenic bacteria, and hence are considered a promising substrate for hydrogen production in microbial electrolysis cells (MECs). These fermentation products have different mechanisms and thermodynamics for their anaerobic oxidation, and therefore the composition of fermentation effluent significantly influences MEC performance. This study examined the microbial electrolysis of a synthetic fermentation effluent (containing acetate, propionate, butyrate, lactate, and ethanol) in two-chamber MECs fitted with either a proton exchange membrane (PEM) or an anion exchange membrane (AEM), with a focus on the utilization preference between the electron sources present in the effluent. Throughout the eight cycles of repeated batch operation with an applied voltage of 0.8 V, the AEM-MECs consistently outperformed the PEM-MECs in terms of organic removal, current generation, and hydrogen production. The highest hydrogen yield achieved for AEM-MECs was 1.26 L/g chemical oxygen demand (COD) fed (approximately 90% of the theoretical maximum), which was nearly double the yield for PEM-MECs (0.68 L/g COD fed). The superior performance of AEM-MECs was attributed to the greater pH imbalance and more acidic anodic pH in PEM-MECs (5.5–6.0), disrupting anodic respiration. Although butyrate is more thermodynamically favorable than propionate for anaerobic oxidation, butyrate was the least favored electron source, followed by propionate, in both AEM- and PEM-MECs, while ethanol and lactate were completely consumed. Further research is needed to better comprehend the preferences for different electron sources in fermentation effluents and enhance their microbial electrolysis.