Bioelectrochemical systems (BESs) are hybrid systems using electroactive bacteria and solid electrodes, which serve as electron donor or acceptor for microorganisms. When forming a biofilm on the electrode, bacteria secrete extracellular polymeric substances (EPSs). However, EPS excretion of electroactive biofilms in BES has been rarely studied so far. Consequently, the aim of this study is to develop a routine including the electrochemical cultivation, biofilm harvesting, fractionation, and biochemical analysis of the EPS secreted by Geobacter sulfurreducens under electroactive conditions. G. sulfurreducens was cultivated in microbial fuel cell mode on graphite-based electrodes polarized to +400 mV versus Ag/AgCl for 8 d. A maximum current density of 172 ± 29 μA cm–2 was reached after 7 d. The EPS secreted from the biofilms were harvested and fractioned into soluble, loosely bound, and tightly bound EPS and biochemically analyzed. Electroactive cultures secreted significantly more EPSs compared to cells grown under standard heterotrophic conditions (fumarate respiration). With 116 pg per cell, the highest amount of EPSs was measured for the soluble EPS fraction of G. sulfurreducens using anodic respiration, followed by the tightly bound (18 pg cell–1) and loosely bound (11 pg cell–1) fractions of the EPS. Proteins were found to dominate all EPS fractions of the biofilms grown under electrochemical conditions. To the best of the authors’ knowledge, these experiments are the first approach toward a complete analysis of the main EPS components of G. sulfurreducens under anode-respiring conditions.

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CO2 has been electrochemically reduced to the intermediate formate, which was subsequently used as sole substrate for the production of the polymer polyhydroxybutyrate (PHB) by the microorganism Cupriavidus necator. Faradaic efficiencies (FE) up to 54 % have been reached with Sn‐based gas‐diffusion electrodes in physiological electrolyte. The formate containing electrolyte can be used directly as drop‐in solution in the following biological polymer production by resting cells. 56 mg PHB L−1 and a ratio of 34 % PHB per cell dry weight were achieved. The calculated overall FE for the process was as high as 4 %. The direct use of the electrolyte as drop‐in media in the bioconversion enables simplified processes with a minimum of intermediate purification effort. Thus, an optimal coupling between electrochemical and biotechnological processes can be realized.

Shewanella oneidensis is one of the best-understood model organisms for extracellular electron transfer. Endogenously produced and exported flavin molecules seem to play an important role in this process and mediate the connection between respiratory enzymes on the cell surface and the insoluble substrate by acting as electron shuttle and cytochrome-bound cofactor. Consequently, the addition of riboflavin to a bioelectrochemical system (BES) containing S. oneidensis cells as biocatalyst leads to a strong current increase. Still, an external application of riboflavin to increase current production in continuously operating BESs does not seem to be applicable due to the constant washout of the soluble flavin compound. In this study, we developed a recyclable electron shuttle to overcome the limitation of mediator addition to BES. Riboflavin was coupled to magnetic beads that can easily be recycled from the medium. The effect on current production and cell distribution in a BES as well as the recovery rate and the stability of the beads was investigated. The addition of synthesized beads leads to a more than twofold higher current production, which was likely caused by increased biofilm production. Moreover, 90% of the flavin-coupled beads could be recovered from the BESs using a magnetic separator.

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Various enzymes utilize hydrogen peroxide as an oxidant. Such “peroxizymes” are potentially very attractive catalysts for a broad range of oxidation reactions. Most peroxizymes, however, are inactivated by an excess of H2O2. The electrochemical reduction of oxygen can be used as an in situ generation method for hydrogen peroxide to drive the peroxizymes at high operational stabilities. Using conventional electrode materials, however, also necessitates significant overpotentials, thereby reducing the energy efficiency of these systems. This study concerns a method to coat a gas‐diffusion electrode with oxidized carbon nanotubes (oCNTs), thereby greatly reducing the overpotential needed to perform an electroenzymatic halogenation reaction. In comparison to the unmodified electrode, with the oCNTs‐modified electrode the overpotential can be reduced by approximately 100 mV at comparable product formation rates.

Geopolymer (GP) inorganic binders have a superior acid resistance compared to conventional cement (e.g., Portland cement, PC) binders, have better microbial compatibility, and are suitable for introducing electrically conductive additives to improve electron and ion transfer properties. In this study, GP–graphite (GPG) composites and PC–graphite (PCG) composites with a graphite content of 1–10 vol % were prepared and characterized. The electrical conductivity percolation threshold of the GPG and PCG composites was around 7 and 8 vol %, respectively. GPG and PCG composites with a graphite content of 8 to 10 vol % were selected as anode electrodes for the electrochemical analysis in two-chamber polarized microbial fuel cells (MFCs). Graphite electrodes were used as the positive control reference material. Geobacter sulfurreducens was used as a biofilm-forming and electroactive model organism for MFC experiments. Compared to the conventional graphite anodes, the anode-respiring biofilms resulted in equal current production on GPG composite anodes, whereas the PCG composites showed a very poor performance. The largest mean value of the measured current densities of a GPG composite used as anodes in MFCs was 380.4 μA cm–2 with a standard deviation of 129.5 μA cm–2. Overall, the best results were obtained with electrodes having a relatively low Ohmic resistance, that is, GPG composites and graphite. The very first approach employing sustainable GPs as a low-cost electrode binder material in an MFC showed promising results with the potential to greatly reduce the production costs of MFCs, which would also increase the feasibility of MFC large-scale applications.

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