Ludovic Jourdin

A novel carbon nanotube modified scaffold as an efficient biocathode material for improved microbial electrosynthesis

We report on a novel biocompatible, highly conductive three-dimensional cathode manufactured by direct growth of flexible multiwalled carbon nanotubes on reticulated vitreous carbon (NanoWeb-RVC) for the improvement of microbial bioelectrosynthesis (MES). NanoWeb-RVC allows for an enhanced bacterial attachment and biofilm development within its hierarchical porous structure. 1.7 and 2.6 fold higher current density and acetate bioproduction rate normalized to total surface area were reached on NanoWeb-RVC versus a carbon plate control for the microbial reduction of carbon dioxide by mixed cultures. This is the first study showing better intrinsic efficiency as biocathode material of a three-dimensional electrode versus a flat electrode: this comparison has been made considering the total surface area of the porous electrode, and not just the projected surface area. Therefore, the improved performance is attributed to the nanostructure of the electrode and not to an increase in surface area. Unmodified reticulated vitreous carbon electrodes lacking the nanostructure were found unsuitable for MES, with no biofilm development and no acetate production detected. The high surface area to volume ratio of the macroporous RVC maximizes the available biofilm area while ensuring effective mass transfer to and from the biofilm. The nanostructure enhances the bacteria-electrode interaction and microbial extracellular electron transfer. When normalized to projected surface area, current densities and acetate production rates of 3.7 mA cm−2 and 1.3 mM cm−2 d−1, respectively, were reached, making the NanoWeb-RVC an extremely efficient material from an engineering perspective as well. These values are the highest reported for any MES system to date.

High Acetic Acid Production Rate Obtained by Microbial Electrosynthesis from Carbon Dioxide

High product specificity and production rate are regarded as key success parameters for large-scale applicability of a (bio)chemical reaction technology. Here, we report a significant performance enhancement in acetate formation from CO2, reaching comparable productivity levels as in industrial fermentation processes (volumetric production rate and product yield). A biocathode current density of -102 ± 1 A m(-2) and an acetic acid production rate of 685 ± 30 (g m(-2) day(-1)) have been achieved in this study. High recoveries of 94 ± 2% of the CO2 supplied as the sole carbon source and 100 ± 4% of electrons into the final product (acetic acid) were achieved after development of a mature biofilm, reaching an elevated product titer of up to 11 g L(-1). This high product specificity is remarkable for mixed microbial cultures, which would make the product downstream processing easier and the technology more attractive. This performance enhancement was enabled through the combination of a well-acclimatized and enriched microbial culture (very fast start-up after culture transfer), coupled with the use of a newly synthesized electrode material, EPD-3D. The throwing power of the electrophoretic deposition technique, a method suitable for large-scale production, was harnessed to form multiwalled carbon nanotube coatings onto reticulated vitreous carbon to generate a hierarchical porous structure.

Bringing High-Rate, CO2-Based Microbial Electrosynthesis Closer to Practical Implementation through Improved Electrode Design and Operating Conditions.

The enhancement of microbial electrosynthesis (MES) of acetate from CO2 to performance levels that could potentially support practical implementations of the technology must go through the optimization of key design and operating conditions. We report that higher proton availability drastically increases the acetate production rate, with pH 5.2 found to be optimal, which will likely suppress methanogenic activity without inhibitor addition. Applied cathode potential as low as -1.1 V versus SHE still achieved 99% of electron recovery in the form of acetate at a current density of around -200 A m(-2). These current densities are leading to an exceptional acetate production rate of up to 1330 g m(-2) day(-1) at pH 6.7. Using highly open macroporous reticulated vitreous carbon electrodes with macropore sizes of about 0.6 mm in diameter was found to be optimal for achieving a good balance between total surface area available for biofilm formation and effective mass transfer between the bulk liquid and the electrode and biofilm surface. Furthermore, we also successfully demonstrated the use of a synthetic biogas mixture as carbon dioxide source, yielding similarly high MES performance as pure CO2. This would allow this process to be used effectively for both biogas quality improvement and conversion of the available CO2 to acetate.

Autotrophic hydrogen-producing biofilm growth sustained by a cathode as the sole electron and energy source

It is still unclear whether autotrophic microbial biocathode biofilms are able to self-regenerate under purely cathodic conditions without any external electron or organic carbon sources. Here we report on the successful development and long-term operation of an autotrophic biocathode whereby an electroactive biofilm was able to grow and sustain itself with CO2 as a sole carbon source and using the cathode as electron source, with H2 as sole product. From a small inoculum of 15 mg COD (in 250 mL), containing 30.3% Archaea, the bioelectrochemical system operating at -0.5 V vs. SHE enabled an estimated biofilm growth of 300 mg as COD over a period of 276 days. A dramatic change in the microbial population was observed during this period with Archaea disappearing completely (<0.1% of population). The predominant phyla enriched were Proteobacteria (57.3%), Firmicutes (12.4%), Bacteroidetes (11.6%) and Actinobacteria (1.1%). Up to 9.2 L H2 m(-2) day(-1) (1.88 A m(-2)) was achieved when the cathode potential was decreased to -0.75 V vs. SHE. This study demonstrates that purely autotrophic biofilm growth coupled to proton reduction to hydrogen alone can be sustained with a cathode as the sole electron source, while avoiding the development of H2-consuming microorganisms such as methanogens and acetogens.

Methanobacterium enables high rate electricity-driven autotrophic sulfate reduction

Correction for ‘Methanobacterium enables high rate electricity-driven autotrophic sulfate reduction’ by Guillermo Pozo et al., RSC Adv., 2015, 5, 89368–89374.

Critical biofilm growth throughout unmodified carbon felts allows continuous bioelectrochemical chain elongation from CO2 up to caproate at high current density

Current challenges for microbial electrosynthesis include the production of higher value chemicals than acetate, at high rates, using cheap electrode materials. We demonstrate here the continuous, biofilm-driven production of acetate (C2), n butyrate (nC4), and n-caproate (nC6) from sole CO2 on unmodified carbon felt electrodes. No other organics were detected. This is the first quantified continuous demonstration of n-caproate production from CO2 using an electrode as sole electron donor. During continuous nutrients supply mode a thick biofilm was developed covering the whole thickness of the felt (1.2 cm deep), which coincided with high current densities and organics production rates. Current density reached up to -14 kA m-3electrode (-175 A m-2). Maximum sustained production rates of 9.8 ± 0.65 g L-1 day-1 C2, 3.2 ± 0.1 g L-1 day-1 nC4, and 0.95 ± 0.05 g L-1 day-1 nC6 were achieved (averaged between duplicates), at electron recoveries of 60-100%. Scanning electron micrographs revealed a morphologically highly diverse biofilm with long filamentous microorganism assemblies (~400 µm). n-Caproate is a valuable chemical for various industrial application, e.g. it can be used as feed additives or serve as precursor for liquid biofuels production.