Carbon dioxide utilization is a key strategy for sustainable chemical production and climate change mitigation. Microbial electrosynthesis (MES) offers a promising approach to convert CO₂ into organic acids and multi‑carbon compounds, but its industrial application requires improved product recovery methods. In this study, we developed an integrated MES-sorption-distillation system for the recovery of pure hexanoic acid. Adsorption experiments identified conditions for C6-selective capture from C2–C6 carboxylate mixtures typically produced from MES. Subsequent desorption using CO₂ expanded methanol enriched hexanoic acid concentration by 13-fold compared to the aqueous feed, achieving 67 % recovery in a single pass, but 100 % overall, since recirculation of unrecovered carboxylates back to the MES reactor is proposed. This recirculation will enhance chain elongation, eliminate loss of unrecovered carboxylates, and reduce the need for external pH control during MES. Distillation of the desorbed mixture led to streams of pure products and reusable solvent, without losses. Notably, 87 % of the total energy demand for product formation is attributed to the MES stage, where electrical energy is directly supplied as electrons to drive microbial production. Thus, MES with the proposed recovery method enables pure hexanoic acid production with minimal losses of materials or energy and potentially allows the system to operate in a carbon-negative manner.

Syngas fermentation is a promising bioprocessing method that utilises autotrophic organisms to convert C1 gases, such as CO and CO2, into valuable chemicals, offering both environmental and economic benefits. Despite these advantages, the industrial application of gas fermentation remains limited owing to challenges in productivity associated with gas substrates. While previous studies have focused on optimizing reactor design, mass transfer, and growth medium as solutions to these specific challenges, the direct correlation between cell viability and productivity remains unexplored. To address this gap, this study investigates the viability of the acetogenic strain Eubacterium callanderi KIST612 and its impact on acetate production across various operational modes. Unlike conventional single-reactor systems, a dual-reactor strategy was implemented to enhance viable cell retention, leading to improved process efficiency. This approach significantly increased the total carbon conversion rate to 9.30mmolh-1 and the specific productivity of viable cells to 0.13g gcell-1h-1, ultimately achieving the highest acetate titer (34.4gL-1) with >53% cell viability. These findings represent a major advancement over previous studies, demonstrating that maintaining cell viability is critical for optimizing acetate productivity. By integrating viability control into process operations, this study presents a scalable and efficient strategy to enhance gas fermentation performance, improve substrate conversion efficiency, and expand biochemical production potential for industrial applications.