Electricity generation using an air-cathode single chamber microbial fuel cell in the presence and absence of a proton exchange membrane

Microbial fuel cells (MFCs) are typically designed as a two-chamber system with the bacteria in the anode chamber separated from the cathode chamber by a polymeric proton exchange membrane (PEM). Most MFCs use aqueous cathodes where water is bubbled with air to provide dissolved oxygen to electrode. To increase energy output and reduce the cost of MFCs, we examined power generation in an air-cathode MFC containing carbon electrodes in the presence and absence of a polymeric proton exchange membrane (PEM). Bacteria present in domestic wastewater were used as the biocatalyst, and glucose and wastewater were tested as substrates. Power density was found to be much greater than typically reported for aqueous-cathode MFCs, reaching a maximum of 262 +/- 10 mW/m2 (6.6 +/- 0.3 mW/L; liquid volume) using glucose. Removing the PEM increased the maximum power density to 494 +/- 21 mW/m2 (12.5 +/- 0.5 mW/L). Coulombic efficiency was 40-55% with the PEM and 9-12% with the PEM removed, indicating substantial oxygen diffusion into the anode chamber in the absence of the PEM. Power output increased with glucose concentration according to saturation-type kinetics, with a half saturation constant of 79 mg/L with the PEM-MFC and 103 mg/L in the MFC without a PEM (1000 omega resistor). Similar results on the effect of the PEM on power density were found using wastewater, where 28 +/- 3 mW/m2 (0.7 +/- 0.1 mW/L) (28% Coulombic efficiency) was produced with the PEM, and 146 +/- 8 mW/m2 (3.7 +/- 0.2 mW/L) (20% Coulombic efficiency) was produced when the PEM was removed. The increase in power output when a PEM was removed was attributed to a higher cathode potential as shown by an increase in the open circuit potential. An analysis based on available anode surface area and maximum bacterial growth rates suggests that mediatorless MFCs may have an upper order-of-magnitude limit in power density of 10(3) mW/m2. A cost-effective approach to achieving power densities in this range will likely require systems that do not contain a polymeric PEM in the MFC and systems based on direct oxygen transfer to a carbon cathode.     

Power densities using different cathode catalysts (Pt and CoTMPP) and polymer binders (nafion and PTFE) in single chamber microbial fuel cells

Cathode catalysts and binders were examined for their effect on power densities in single chamber, air-cathode, microbial fuel cells (MFCs). Chronopotentiometry tests indicated thatthe cathode potential was only slightly reduced (20-40 mV) when Pt loadings were decreased from 2 to 0.1 mg cm(-2), and that Nafion performed better as a Pt binder than poly(tetrafluoroethylene) (PTFE). Replacing the precious-metal Pt catalyst (0.5 mg cm(-2); Nafion binder) with a cobalt material (cobalt tetramethylphenylporphyrin, CoTMPP) produced slightly improved cathode performance above 0.6 mA cm(-2), but reduced performance (<40 mV) at lower current densities. MFC fed batch tests conducted for 35 cycles (31 days) using glucose showed that replacement of the Nafion binder used for the cathode catalyst (0.5 mg of Pt cm(-2)) with PTFE reduced the maximum power densities (from 400 +/- 10 to 480 +/- 20 mW m(-2) to 331 +/- 3 to 360 +/- 10 mW m(-2)). When the Pt loading on cathode was reduced to 0.1 mg cm(-2), the maximum power density of MFC was reduced on average by 19% (379 +/- 5 to 301 +/- 15 mW m(-2); Nafion binder). Power densities with CoTMPP were only 12% (369 +/- 8 mW m(-2)) lower over 25 cycles than those obtained with Pt (0.5 mg cm(-2); Nafion binder). Power densities obtained using with catalysts on the cathodes were approximately 4 times more than those obtained using a plain carbon electrode. These results demonstrate that cathodes used in MFCs can contain very little Pt, and that the Pt can even be replaced with a non-precious metal catalyst such as a CoTMPP with only slightly reduced performance.     

Graphite fiber brush anodes for increased power production in air-cathode microbial fuel cells

To efficiently generate electricity using bacteria in microbial fuel cells (MFCs), highly conductive noncorrosive materials are needed that have a high specific surface area (surface area per volume) and an open structure to avoid biofouling. Graphite brush anodes, consisting of graphite fibers wound around a conductive, but noncorrosive metal core, were examined for power production in cube (C-MFC) and bottle (B-MFC) air-cathode MFCs. Power production in C-MFCs containing brush electrodes at 9600 m2/m3 reactor volume reached a maximum power density of 2400 mW/m2 (normalized to the cathode projected surface area), or 73 W/m3 based on liquid volume, with a maximum Coulombic efficiency (CE) of 60%. This power density, normalized by cathode projected area, is the highest value yet achieved by an air-cathode system. The increased power resulted from a reduction in internal resistance from 31 to 8 Q. Brush electrodes (4200 m2/m3) were also tested in B-MFCs, consisting of a laboratory media bottle modified to have a single side arm with a cathode clamped to its end. B-MFCs inoculated with wastewater produced up to 1430 mW/m2 (2.3 W/m3, CE = 23%) with brush electrodes, versus 600 mW/m2 with a plain carbon paper electrode. These findings show that brush anodes that have high surface areas and a porous structure can produce high power densities, and therefore have qualities that make them ideal for scaling up MFC systems.     

Electricity production from cellulose in a microbial fuel cell using a defined binary culture

Microbial fuel cells (MFCs) convert biodegradable materials into electricity, potentially contributing to an array of renewable energy production strategies tailored for specific applications. Since there are no known microorganisms that can both metabolize cellulose and transfer electrons to solid extracellular substrates, the conversion of cellulosic biomass to electricity requires a syntrophic microbial community that uses an insoluble electron donor (cellulose) and electron acceptor (anode). Electricity was generated from cellulose in an MFC using a defined coculture of the cellulolytic fermenter Clostridium cellulolyticum and the electrochemically active Geobacter sulfurreducens. In fed-batch tests using two-chamber MFCs with ferricyanide as the catholyte, the coculture achieved maximum power densities of 143 mW/ m2 (anode area) and 59.2 mW/m2 from 1 g/L carboxymethyl cellulose (CMC) and MN301 cellulose, respectively. Neither pure culture alone produced electricity from these substrates. The coculture increased CMC degradation from 42% to 64% compared to a pure C. cellulolyticum culture. COD removal using CMC and MN301 was 38 and 27%, respectively, with corresponding Coulombic efficiencies of 47 and 39%. Hydrogen, acetate, and ethanol were the main residual metabolites of the binary culture. Cellulose conversion to electricity was also demonstrated using an uncharacterized mixed culture from activated sludge with an aerobic aqueous cathode.     

Production of electricity during wastewater treatment using a single chamber microbial fuel cell

Microbial fuel cells (MFCs) have been used to produce electricity from different compounds, including acetate, lactate, and glucose. We demonstrate here that it is also possible to produce electricity in a MFC from domestic wastewater, while atthe same time accomplishing biological wastewater treatment (removal of chemical oxygen demand; COD). Tests were conducted using a single chamber microbial fuel cell (SCMFC) containing eight graphite electrodes (anodes) and a single air cathode. The system was operated under continuous flow conditions with primary clarifier effluent obtained from a local wastewater treatment plant. The prototype SCMFC reactor generated electrical power (maximum of 26 mW m(-2)) while removing up to 80% of the COD of the wastewater. Power output was proportional to the hydraulic retention time over a range of 3-33 h and to the influent wastewater strength over a range of 50-220 mg/L of COD. Current generation was controlled primarily by the efficiency of the cathode. Optimal cathode performance was obtained by allowing passive air flow rather than forced air flow (4.5-5.5 L/min). The Coulombic efficiency of the system, based on COD removal and current generation, was < 12% indicating a substantial fraction of the organic matter was lost without current generation. Bioreactors based on power generation in MFCs may represent a completely new approach to wastewater treatment. If power generation in these systems can be increased, MFC technology may provide a new method to offset wastewater treatment plant operating costs, making advanced wastewater treatment more affordable for both developing and industrialized nations.     

Production of electricity from acetate or butyrate using a single-chamber microbial fuel cell

Hydrogen can be recovered by fermentation of organic material rich in carbohydrates, but much of the organic matter remains in the form of acetate and butyrate. An alternative to methane production from this organic matter is the direct generation of electricity in a microbial fuel cell (MFC). Electricity generation using a single-chambered MFC was examined using acetate or butyrate. Power generated with acetate (800 mg/L) (506 mW/m2 or 12.7 mW/ L) was up to 66% higher than that fed with butyrate (1000 mg/L) (305 mW/m2 or 7.6 mW/L), demonstrating that acetate is a preferred aqueous substrate for electricity generation in MFCs. Power output as a function of substrate concentration was well described by saturation kinetics, although maximum power densities varied with the circuit load. Maximum power densities and half-saturation constants were Pmax = 661 mW/m2 and Ks = 141 mg/L for acetate (218 ohms) and Pmax = 349 mW/m2 and Ks = 93 mg/L for butyrate (1000 ohms). Similar open circuit potentials were obtained in using acetate (798 mV) or butyrate (795 mV). Current densities measured for stable power outputwere higher for acetate (2.2 A/m2) than those measured in MFCs using butyrate (0.77 A/m2). Cyclic voltammograms suggested that the main mechanism of power production in these batch tests was by direct transfer of electrons to the electrode by bacteria growing on the electrode and not by bacteria-produced mediators. Coulombic efficiencies and overall energy recovery were 10-31 and 3-7% for acetate and 8-15 and 2-5% for butyrate, indicating substantial electron and energy losses to processes other than electricity generation. These results demonstrate that electricity generation is possible from soluble fermentation end products such as acetate and butyrate, but energy recoveries should be increased to improve the overall process performance.     

Power generation in fed-batch microbial fuel cells as a function of ionic strength, temperature, and reactor configuration

Power density, electrode potential, coulombic efficiency, and energy recovery in single-chamber microbial fuel cells (MFCs) were examined as a function of solution ionic strength, electrode spacing and composition, and temperature. Increasing the solution ionic strength from 100 to 400 mM by adding NaCl increased power output from 720 to 1330 mW/m2. Power generation was also increased from 720 to 1210 mW/m2 by decreasing the distance between the anode and cathode from 4to 2 cm. The power increases due to ionic strength and electrode spacing resulted from a decrease in the internal resistance. Power output was also increased by 68% by replacing the cathode (purchased from a manufacturer) with our own carbon cloth cathode containing the same Pt loading. The performance of conventional anaerobic treatment processes, such as anaerobic digestion, are adversely affected by temperatures below 30 degrees C. However, decreasing the temperature from 32 to 20 degrees C reduced power output by only 9%, primarily as a result of the reduction of the cathode potential. Coulombic efficiencies and overall energy recovery varied as a function of operating conditions, but were a maximum of 61.4 and 15.1% (operating conditions of 32 degrees C, carbon paper cathode, and the solution amended with 300 mM NaCl). These results, which demonstrate that power densities can be increased to over 1 W/m2 by changing the operating conditions or electrode spacing, should lead to further improvements in power generation and energy recovery in single-chamber, air-cathode MFCs.     

Increased power generation in a continuous flow MFC with advective flow through the porous anode and reduced electrode spacing

The maximum power generated in a single-chamber air-cathode microbial fuel cell (MFC) has previously been shown to increase when the spacing between the electrodes is decreased from 4 to 2 cm. However, the maximum power from a MFC with glucose (500 mg/L) decreased from 811 mW/ m2 (R(ex) = 200 omega, Coulombic efficiency of CE = 28%) to 423 mW/m2 (R(ex) = 500 omega, CE = 18%) when the electrode spacing was decreased from 2 to 1 cm (batch mode operation, power normalized by cathode projected area). This decrease in power was unexpected as the internal resistance decreased from 35 omega (2-cm spacing) to 16 omega (1-cm spacing). However, providing advective flow through the porous anode toward the cathode substantially increased power, resulting in the highest maximum power densities yet achieved in an air-cathode system using glucose or domestic wastewater as substrates. For glucose, with a 1-cm electrode spacing and flow through the anode with continuous flow operation of the MFC, the maximum power increased to 1540 mW/m2 (51 W/m3) and the CE increased to 60%. Using domestic wastewater (255 +/- 10 mg of COD/L), the maximum power density was 464 mW/m2 (15.5 W/m3; CE = 27%). Although flow through the anode could lead to plugging, especially for particulate substrates such as domestic wastewater, the system was operated using glucose for over 42 days without clogging. These results show that power output in this air-cathode single-chamber MFC can be increased by reducing the electrode spacing if the reactors are operated in continuous flow mode with advective flow through the anode toward the cathode.     

Enhanced electricity production by use of reconstituted artificial consortia of estuarine bacteria grown as biofilms

Microbial fuel cells (MFCs) can convert organic compounds directly into electricity by catalytic oxidation, and although MFCs have attracted considerable interest, there is little information on the electricity-generating potential of artificial bacterial biofilms. We have used acetate-fed MFCs inoculated with sediment, with two-chamber bottles and carbon cloth electrodes to deliver a maximum power output of ~175 mW · m(-2) and a stable power output of ~105 mW · m(-2). Power production was by direct transfer of electrons to the anode from bacterial consortia growing on the anode, as confirmed by cyclic voltammetry (CV) and scanning electron microscopy (SEM). Twenty different species (74 strains) of bacteria were isolated from the consortium under anaerobic conditions and cultured in the laboratory, of which 34% were found to be exoelectrogens in single-species studies. Exoelectrogenesis by members of the genera Vibrio , Enterobacter , and Citrobacter and by Bacillus stratosphericus was confirmed, by use of culture-based methods, for the first time. An MFC with a natural bacterial consortium showed higher power densities than those obtained with single strains. In addition, the maximum power output could be further increased to ~200 mW · m(-2) when an artificial consortium consisting of the best 25 exoelectrogenic isolates was used, demonstrating the potential for increased performance and underlying the importance of artificial biofilms for increasing power output.     

Microbial fuel cells for sulfide removal

Thus far, microbial fuel cells (MFCs) have been used to convert carbon-based substrates to electricity. However, sulfur compounds are ubiquitously present in organic waste and wastewater. In this study, a MFC with a hexacyanoferrate cathodic electrolyte was used to convert dissolved sulfide to elemental sulfur. Two types of MFCs were used, a square type closed to the air and a tubular type in which the cathode compartment was open to the air. The square-type MFCs demonstrated a potential-dependent conversion of sulfide to sulfur. In the tubular system, up to 514 mg sulfide L(-1) net anodic compartment (NAC) day(-1) (241 mg L(-1) day(-1) total anodic compartment, TAC) was removed. The sulfide oxidation in the anodic compartment resulted in electricity generation with power outputs up to 101 mW L(-1) NAC (47 W m(-3) TAC). Microbial fuel cells were coupled to an anaerobic upflow anaerobic sludge blanket reactor, providing total removals of up to 98% and 46% of the sulfide and acetate, respectively. The MFCs were capable of simultaneously removing sulfate via sulfide. This demonstrates that digester effluents can be polished by a MFC for both residual carbon and sulfur compounds. The recovery of electrons from sulfides implies a recovery of energy otherwise lost in the methane digester.