Benjamin Erable

Microbial fuel cells: From fundamentals to applications. A review

In the past 10–15 years, the microbial fuel cell (MFC) technology has captured the attention of the scientific community for the possibility of transforming organic waste directly into electricity through microbially catalyzed anodic, and microbial/enzymatic/abiotic cathodic electrochemical reactions. In this review, several aspects of the technology are considered. Firstly, a brief history of abiotic to biological fuel cells and subsequently, microbial fuel cells is presented. Secondly, the development of the concept of microbial fuel cell into a wider range of derivative technologies, called bioelectrochemical systems, is described introducing briefly microbial electrolysis cells, microbial desalination cells and microbial electrosynthesis cells. The focus is then shifted to electroactive biofilms and electron transfer mechanisms involved with solid electrodes. Carbonaceous and metallic anode materials are then introduced, followed by an explanation of the electro catalysis of the oxygen reduction reaction and its behavior in neutral media, from recent studies. Cathode catalysts based on carbonaceous, platinum-group metal and platinum-group-metal-free materials are presented, along with membrane materials with a view to future directions. Finally, microbial fuel cell practical implementation, through the utilization of energy output for practical applications, is described.

Microbial Catalysis of the Oxygen Reduction Reaction for Microbial Fuel Cells: A Review

The slow kinetics of the electrochemical oxygen reduction reaction (ORR) is a crucial bottleneck in the development of microbial fuel cells (MFCs). This article firstly gives an overview of the particular constraints imposed on ORR by MFC operating conditions: neutral pH, slow oxygen mass transfer, sensitivity to reactive oxygen species, fouling and biofouling. A review of the literature is then proposed to assess how microbial catalysis could afford suitable solutions. Actually, microbial catalysis of ORR occurs spontaneously on the surface of metallic materials and is an effective motor of microbial corrosion. In this framework, several mechanisms have been proposed, which are reviewed in the second part of the article. The last part describes the efforts made in the domain of MFCs to determine the microbial ecology of electroactive biofilms and define efficient protocols for the formation of microbial oxygen-reducing cathodes. Although no clear mechanism has been established yet, several promising solutions have been recently proposed.

Marine aerobic biofilm as biocathode catalyst.

Stainless steel electrodes were immersed in open seawater and polarized for some days at -200 mV vs. Ag/AgCl. The current increase indicated the formation of biofilms that catalysed the electrochemical reduction of oxygen. These wild, electrochemically active (EA) biofilms were scraped, resuspended in seawater and used as the inoculum in closed 0.5L electrochemical reactors. This procedure allowed marine biofilms that are able to catalyse oxygen reduction to be formed in small, closed small vessels for the first time. Potential polarisation during biofilm formation was required to obtain EA biofilms and the roughness of the surface favoured high current values. The low availability of nutrients was shown to be a main limitation. Using an open reactor continuously fed with filtered seawater multiplied the current density by a factor of around 20, up to 60 microA/cm(2), which was higher than the current density provided in open seawater by the initial wild biofilm. These high values were attributed to continuous feeding with the nutrients contained in seawater and to suppression of the indigenous microbial species that compete with EA strains in natural open environments. Pure isolates were extracted from the wild biofilms and checked for EA properties. Of more than thirty different species tested, only Winogradskyella poriferorum and Acinetobacter johsonii gave current densities of respectively 7% and 3% of the current obtained with the wild biofilm used as inoculum. Current densities obtained with pure cultures were lower than those obtained with wild biofilms. It is suspected that synergic effects occur in whole biofilms or/and that wild strains may be more efficient than the cultured isolates.

Stainless steel is a promising electrode material for anodes of microbial fuel cells

The abilities of carbon cloth, graphite plate and stainless steel to form microbial anodes were compared under identical conditions. Each electrode was polarised at −0.2 V vs. SCE in soil leachate and fed by successive additions of 20 mM acetate. Under these conditions, the maximum current densities provided were on average 33.7 A m−2 for carbon cloth, 20.6 A m−2 for stainless steel, and 9.5 A m−2 for flat graphite. The high current density obtained with carbon cloth was obviously influenced by the three-dimensional electrode structure. Nevertheless, a fair comparison between flat electrodes demonstrated the great interest of stainless steel. The comparison was even more in favour of stainless steel at higher potential values. At +0.1 V vs. SCE stainless steel provided up to 35 A m−2, while graphite did not exceed 11 A m−2. This was the first demonstration that stainless steel offers a very promising ability to form microbial anodes. The surface topography of the stainless steel did not significantly affect the current provided. Analysis of the voltammetry curves allowed two groups of electrode materials to be distinguished by their kinetics. The division into two well-defined kinetics groups proved to be appropriate for a wide range of microbial anodes described in the literature.

Application of electro-active biofilms

The concept of an electro-active biofilm (EAB) has recently emerged from a few studies that discovered that certain bacteria which form biofilms on conductive materials can achieve a direct electrochemical connection with the electrode surface using it as electron exchanger, without the aid of mediators. This electro-catalytic property of biofilms has been clearly related to the presence of some specific strains that are able to exchange electrons with solid substrata (eg Geobacter sulfurreducens and Rhodoferax ferrireducens). EABs can be obtained principally from natural sites such as soils or seawater and freshwater sediments or from samples collected from a wide range of different microbially rich environments (sewage sludge, activated sludge, or industrial and domestic effluents). The capability of some microorganisms to connect their metabolisms directly in an external electrical power supply is very exciting and extensive research is in progress on exploring the possibilities of EABs applications. Indeed, the best known application is probably the microbial fuel cell technology that is capable of turning biomass into electrical energy. Nevertheless, EABs coated onto electrodes have recently become popular in other fields like bioremediation, biosynthesis processes, biosensor design, and biohydrogen production.

Stainless steel foam increases the current produced by microbial bioanodes in bioelectrochemical systems

Stainless steel is gaining increasing interest as an anodic material in bioelectrochemical systems and beginning to challenge the more conventional carbon-based materials. Here, microbial bioanodes designed under optimal conditions on carbon cloths gave high current densities, 33.5 + 4.5 A m−2 at −0.2 V/SCE, which were largely outstripped by the current densities of 60 to 80 A m−2 at the same potential and more than 100 A m−2 at 0.0 V/SCE provided by using stainless steel foams.

Ultra microelectrodes increase the current density provided by electroactive biofilms by improving their electron transport ability

Electroactive biofilms were formed from garden compost leachate on platinum wires under constant polarisation at −0.2 V vs.SCE and temperature controlled at 40 °C. The oxidation of 10 mM acetate gave maximum current density of 7 A m−2 with the electrodes of largest diameters (500 and 1000 μm). The smaller diameter wires exhibited an ultra-microelectrode (UME) effect, which increased the maximum current density up to 66 A m−2 with the 25 μm diameter electrode. SEM imaging showed biofilms around 75 μm thick on the 50 μm diameter wire, while they were only 25 μm thick on the 500 μm diameter electrode. Low scan cyclic voltammetry (CV) curves were similar to those already reported for biofilms formed with pure cultures of G. sulfurreducens. Concentrations of the redox molecules contained in the biofilms, which were derived from the non-turnover CVs, were around 0.4 to 0.6 mM, which was close to the value of 1 mM extracted from literature data for G. sulfurreducens biofilms. A numerical model was designed, which demonstrated that the microbial anodes were not controlled here by microbial kinetics. Introducing the concept of average electron transport length made the model well fitted with the experimental results, which indicates rate control by electron transport through the biofilm matrix. According to this model, the UME effect improved the electron transport network in the biofilm, which allowed the biofilm to grow to greater thickness.

Importance of the hydrogen route in up-scaling electrosynthesis for microbial CO2 reduction

Microbial electrochemical reduction of CO2 was carried out under two different applied potentials, −0.36 V and −0.66 V vs. SHE, using a biological sludge as the inoculum. Both potentials were thermodynamically appropriate for converting CO2 to acetate but only −0.66 V enabled hydrogen evolution. No acetate production was observed at −0.36 V, while up to 244 ± 20 mg L−1 acetate was produced at −0.66 V vs. SHE. The same microbial inoculum implemented in gas–liquid contactors with H2 and CO2 gas supply led to acetate production of 2500 mg L−1. When a salt marsh sediment was used as the inoculum, no reduction was observed in the electrochemical reactors, while supplying H2 + CO2 gas led to formate and then acetate production. Finally, pure cultures of Sporomusa ovata grown under H2 and CO2 gas feeding showed acetate production of up to 2904 mg L−1, higher than those reported so far in the literature for S. ovata implemented in bioelectrochemical processes. Unexpected ethanol production of up to 1411 mg L−1 was also observed. All these experimental data confirm that hydrogen produced on the cathode by water electrolysis is an essential mediator in the microbial electrochemical reduction of CO2. Implementing homoacetogenic microbial species in purposely designed gas–liquid biocontactors should now be considered as a relevant strategy for developing CO2 conversion.

Electroanalysis of microbial anodes for bioelectrochemical systems: basics, progress and perspectives

Over about the last ten years, microbial anodes have been the subject of a huge number of fundamental studies dealing with an increasing variety of possible application domains. Out of several thousands of studies, only a minority have used 3-electrode set-ups to ensure well-controlled electroanalysis conditions. The present article reviews these electroanalytical studies with the admitted objective of promoting this type of investigation. A first recall of basics emphasises the advantages of the 3-electrode set-up compared to microbial fuel cell devices if analytical objectives are pursued. Experimental precautions specifically relating to microbial anodes are then noted and the existing experimental set-ups and procedures are reviewed. The state-of-the-art is described through three aspects: the effect of the polarisation potential on the characteristics of microbial anodes, the electroanalytical techniques, and the electrode. We hope that the final outlook will encourage researchers working with microbial anodes to strengthen their engagement along the multiple exciting paths of electroanalysis.

First air-tolerant effective stainless steel microbial anode obtained from a natural marine biofilm.

Microbial anodes were constructed with stainless steel electrodes under constant polarisation. The seawater medium was inoculated with a natural biofilm scraped from harbour equipment. This procedure led to efficient microbial anodes providing up to 4A/m(2) for 10mM acetate oxidation at -0.1 V/SCE. The whole current was due to the presence of biofilm on the electrode surface, without any significant involvement of the abiotic oxidation of sulphide or soluble metabolites. Using a natural biofilm as inoculum ensured almost optimal performance of the biofilm anode as soon as it was set up; the procedure also proved able to form biofilms in fully aerated media, which provided up to 0.7A/m(2). The current density was finally raised to 8.2A per square meter projected surface area using a stainless steel grid. The inoculating procedure used here combined with the control of the potential revealed, for the first time, stainless steel as a very competitive material for forming bioanodes with natural microbial consortia.