Iron-Nicarbazin derived platinum group metal-free electrocatalyst in scalable-size air-breathing cathodes for microbial fuel cells.

In this work, a platinum group metal-free (PGM-free) catalyst based on iron as transitional metal and Nicarbazin (NCB) as low cost organic precursor was synthesized using Sacrificial Support Method (SSM). The catalyst was then incorporated into a large area air-breathing cathode fabricated by pressing with a large diameter pellet die. The electrochemical tests in abiotic conditions revealed that after a couple of weeks of successful operation, the electrode experienced drop in performances in reason of electrolyte leakage, which was not an issue with the smaller electrodes. A decrease in the hydrophobic properties over time and a consequent cathode flooding was suspected to be the cause. On the other side, in the present work, for the first time, it was demonstrated the proof of principle and provided initial guidance for manufacturing MFC electrodes with large geometric areas. The tests in MFCs showed a maximum power density of 1.85 W m-2. The MFCs performances due to the addition of Fe-NCB were much higher compared to the iron-free material. A numerical model using Nernst-Monod and Butler-Volmer equations were used to predict the effect of electrolyte solution conductivity and distance anode-cathode on the overall MFC power output. Considering the existing conditions, the higher overall power predicted was 3.6 mW at 22.2 S m-1 and at inter-electrode distance of 1 cm.

Modelling potential/current distribution in microbial electrochemical systems shows how the optimal bioanode architecture depends on electrolyte conductivity.

The theoretical bases for modelling the distribution of the electrostatic potential in microbial electrochemical systems are described. The secondary potential distribution (i.e. without mass transport limitation of the substrate) is shown to be sufficient to validly address microbial electrolysis cells (MECs). MECs are modelled with two different ionic conductivities of the solution (1 and 5.3 S m(-1)) and two bioanode kinetics (jmax = 5.8 or 34 A m(-2)). A conventional reactor configuration, with the anode and the cathode face to face, is compared with a configuration where the bioanode perpendicular to the cathode implements the electrochemical reaction on its two sides. The low solution conductivity is shown to have a crucial impact, which cancels out the advantages obtained by setting the bioanode perpendicular to the cathode. For the same reason, when the surface area of the anode is increased by multiplying the number of plates, care must be taken not to create too dense anode architecture. Actually, the advantages of increasing the surface area by multiplying the number of plates can be lost through worsening of the electrochemical conditions in the multi-layered anode, because of the increase of the electrostatic potential of the solution inside the anode structure. The model gives the first theoretical bases for scaling up MECs in a rather simple but rigorous way.

Industrially scalable surface treatments to enhance the current density output from graphite bioanodes fueled by real domestic wastewater.

Acid and electrochemical surface treatments of graphite electrode, used individually or in combination, significantly improved the microbial anode current production, by +17% to +56%, in well-regulated and duplicated electroanalytical experimental systems. Of all the consequences induced by surface treatments, the modifications of the surface nano-topography preferentially justify an improvement in the fixation of bacteria, and an increase of the specific surface area and the electrochemically accessible surface of graphite electrodes, which are at the origin of the higher performances of the bioanodes supplied with domestic wastewater. The evolution of the chemical composition and the appearance of C-O, C=O, and O=C-O groups on the graphite surface created by combining acid and electrochemical treatments was prejudicial to the formation of efficient domestic-wastewater-oxidizing bioanodes. The comparative discussion, focused on the positioning of the performances, shows the industrial interest of applying the surface treatment method to the world of bioelectrochemical systems.

Long-term continuous production of H2 in a microbial electrolysis cell (MEC) treating saline wastewater.

A biofilm-based 4 L two chamber microbial electrolysis cell (MEC) was continuously fed with acetate under saline conditions (35 g/L NaCl) for more than 100 days. The MEC produced a biogas highly enriched in H2 (≥90%). Both current (10.6 ± 0.2 A/m(2)Anode or 199.1 ± 4.0 A/m(3)MEC) and H2 production (201.1 ± 7.5 LH2/m(2)Cathode·d or 0.9 ± 0.0 m(3)H2/m(3)MEC·d) rates were highly significant when considering the saline operating conditions. A microbial analysis revealed an important enrichment in the anodic biofilm with five main bacterial groups: 44% Proteobacteria, 32% Bacteroidetes, 18% Firmicutes and 5% Spirochaetes and 1% Actinobacteria. Of special interest is the emergence within the Proteobacteria phylum of the recently described halophilic anode-respiring bacteria Geoalkalibacter (unk. species), with a relative abundance up to 14%. These results provide for the first time a noteworthy alternative for the treatment of saline effluents and continuous production of H2.