Microbial electrosynthesis (MES) systems can convert CO₂ to acetate and other value-added chemicals using electricity as the reducing power. Several electrochemically active redox mediators can enhance interfacial electron transport between bacteria and the electrode in MES systems. In this study, different redox mediators, such as neutral red (NR), 2-hydroxy-1,4-naphthoquinone (HNQ), and hydroquinone (HQ), were compared to facilitate an MES-based CO₂ reduction reaction on the cathode. The mediators, NR and HNQ, improved acetate production from CO₂ (165 mM and 161 mM, respectively) compared to the control (without a mediator = 149 mM), whereas HQ showed lower acetate production (115 mM). On the other hand, when mediators were used, the electron and carbon recovery efficiency decreased because of the presence of bioelectrochemical reduction pathways other than acetate production. Cyclic voltammetry of an MES with such mediators revealed CO₂ reduction to acetate on the cathode surface. These results suggest that the addition of mediators to MES can improve CO₂ conversion to acetate with further optimization in an operating strategy of electrosynthesis processes.

Crude glycerol is a major byproduct in the production of biodiesel and contains a large number of impurities. The transformation of crude glycerol into valuable compounds such as 1,3-propanediol (1,3-PDO) using clean and renewable processes, like bioconversion, is an important task for the future of the chemical industry. In this study, 1,3-PDO bioproductions from crude and pure glycerol were estimated as 15.4 ± 0.8 and 11.4 ± 0.1 mmol/L, respectively. Because 1,3-PDO is a reductive metabolite that requires additional reducing energy, external supplements of electron for further improvement of 1,3-PDO biosynthesis were attempted using a bioelectrochemical system (BES) or zero-valent iron (ZVI). The conversions of crude and pure glycerol under electrode and iron-based cultivation were investigated for 1,3-PDO production accompanied by metabolic shift and cell growth. The BES-based conversion produced 32.6 ± 0.6 mmol/L of 1,3-PDO with ZVI implementation.

The bacterial redox state is essential for controlling the titer and yield of the final metabolites in most bioconversion processes. Glycerol conversion to 1,3-propanediol (PDO) requires a large amount of reducing equivalent and the expression of reductive pathways. Zero-valent iron (ZVI) was used in the glycerol bioconversion of Klebsiella pneumoniae L17. The level of 1,3-PDO production increased with the oxidation of ZVI (31.8 ± 1.2 vs. 25.7 ± 0.5, ZVI vs. no ZVI) while the cellular NADH/NAD⁺ level increased (0.6 vs. 0.3, ZVI vs. no ZVI). X-ray diffraction showed that the iron oxide (Fe₂O₃) was formed during glycerol fermentation. L17 obtained electrons from ZVI and dissolved the iron continuously to form cracks on the surface, suggesting microbially influenced corrosion (MIC) was involved on the surface of ZVI. The ZVI-implemented fermentation shifted bioconversion to a more glycerol-reductive pathway. The qPCR-presented glycerol dehydratase (DhaB) with ZVI implementation was strongly expressed compared to the control. These results suggest that ZVI can contribute to the biotransformation of PDO by inducing intracellular metabolic shifts. This study could also suggest a novel microbial fermentation strategy with the application of MIC.