Investigating microbial fuel cell bioanode performance under different cathode conditions

A compact, three‐in‐one, flow‐through, porous, electrode design with minimal electrode spacing and minimal dead volume was implemented to develop a microbial fuel cell (MFC) with improved anode performance. A biofilm‐dominated anode consortium enriched under a multimode, continuous‐flow regime was used. The increase in the power density of the MFC was investigated by changing the cathode (type, as well as catholyte strength) to determine whether anode was limiting. The power density obtained with an air‐breathing cathode was 56 W/m³ of net anode volume (590 mW/m²) and 203 W/m³ (2160 mW/m²) with a 50‐mM ferricyanide‐based cathode. Increasing the ferricyanide concentration and ionic strength further increased the power density, reaching 304 W/m³ (3220 mW/m², with 200 mM ferricyanide and 200 mM buffer concentration). The increasing trend in the power density indicated that the anode was not limiting and that higher power densities could be obtained using cathodes capable of higher rates of oxidation. The internal solution resistance for the MFC was 5–6 Ω, which supported the improved performance of the anode design. A new parameter defined as the ratio of projected surface area to total anode volume is suggested as a design parameter to relate volumetric and area‐based power densities and to enable comparison of various MFC configurations. Published 2009 American Institute of Chemical Engineers Biotechnol. Prog., 2009     

On the dynamic response of the anode in microbial fuel cells

A study of the dynamic response of a microbial fuel cell (MFC) using membrane electrode assemblies (MEAs) designed for air breathing cathode operation is reported. The MFC used four MEAs simultaneously and has a low internal resistance. An increased concentration of glucose produced a non-linear increase in the maximum current reached. The time to reach the maximum current increased with increasing glucose concentrations of 1-7 mM; varying from approximately 2.4 to 4.2h. The rate at which the current density increased with time was the same for all glucose concentrations up to current densities close to the maximum values. The peak power density varied approximately linearly with glucose concentrations from 2 to 77 mW/m(2) (1-7 mM) with a 1 kΩ resistance. The cell response appeared to be linked to a slow process of fuel transport to the bacteria and their metabolic processes. The dynamic response of the anode was analysed in terms of a substrate mass transport model. The application of different current ranges did not significantly change the dynamic response of either the anode community or the MFC polarization characteristics. Thus, it is likely that the bacterial communities that form under MFC operation contain sufficiently "dominant" electro-active species that are capable of producing high power for MFCs.     

Power output and columbic efficiencies from biofilms of Geobacter sulfurreducens comparable to mixed community microbial fuel cells

It has been previously noted that mixed communities typically produce more power in microbial fuel cells than pure cultures. If true, this has important implications for the design of microbial fuel cells and for studying the process of electron transfer on anode biofilms. To further evaluate this, Geobacter sulfurreducens was grown with acetate as fuel in a continuous flow 'ministack' system in which the carbon cloth anode and cathode were positioned in close proximity, and the cation-selective membrane surface area was maximized in order to overcome some of the electrochemical limitations that were inherent in fuel cells previously employed for the study of pure cultures. Reducing the size of the anode in order to eliminate cathode limitation resulted in maximum current and power densities per m(2) of anode surface of 4.56 A m(-2) and 1.88 W m(-2) respectively. Electron recovery as current from acetate oxidation was c. 100% when oxygen diffusion into the system was minimized. This performance is comparable to the highest levels previously reported for mixed communities in similar microbial fuel cells and slightly higher than the power output of an anaerobic sludge inoculum in the same ministack system. Minimizing the volume of the anode chamber yielded a volumetric power density of 2.15 kW m(-3), which is the highest power density per volume yet reported for a microbial fuel cell. Geobacter sulfurreducens formed relatively uniform biofilms 3-18 mum thick on the carbon cloth anodes. When graphite sticks served as the anode, the current density (3.10 A m(-2)) was somewhat less than with the carbon cloth anodes, but the biofilms were thicker (c. 50 mum) with a more complex pillar and channel structure. These results suggest that the previously observed disparity in power production in pure and mixed culture microbial fuel cell systems can be attributed more to differences in the fuel cell designs than to any inherent superior capability of mixed cultures to produce more power than pure cultures.     

Nitroxide radicals. Controlled release from and transport through biomimetic and hollow fibre membranes

Stable nitroxide radicals have found wide applications in chemistry and biology and they have some potential applications in medicine due to their antioxidant properties. Nitrocellulose filters impregnated with lipid-like substances are used as an imitation of biomembranes and could be used as a controlled drug release vehicle, while experiments with hollow fibres can be useful in the modelling of a drug delivery via blood vessels. This paper describes mechanisms of the nitroxide transport in four different model systems, i.e. a) exit of nitroxide into aqueous solution from porous nitrocellulose filters, impregnated with organic solvents, b) transport of nitroxides through the impregnated membrane from one into another aqueous solution, c) transport of nitroxides from bulk phase of organic solvents through the impregnated membrane into aqueous phase with ascorbic acid, and d) transport of nitroxides from liquid organic phase into aqueous solution through porous hollow fibres. The results are analysed in terms of mass transfer resistance of a membrane, organic and aqueous phase, based on nitroxide diffusion and distribution coefficients. Ascorbic acid reduced nitroxides in water and enhanced the rate of their transfer due to the decrease of transport resistance of unstirred aqueous layers. It is demonstrated that in the case of biomembranes the rate limiting step could be the transport through unstirred aqueous layers and membrane/water interface.     

Oxygen availability effect on the performance of air‐breathing cathode microbial fuel cell

The effect of the oxygen availability over the performance of an air‐breathing microbial fuel cell (MFC) was studied by limiting the oxygen supply to the cathode. It was found that anodic reaction was the limiting stage in the performance of the MFC while oxygen was fully available at cathode. As the cathode was depleted of oxygen, the current density becomes limited by oxygen transport to the electrode surface. The exerted current density was maintained when oxygen mole fraction was higher than 10% due to the very good performance of the cathodic catalysts. However, the current density drastically falls when working at lower concentrations because of mass transfer limitations. In this sense it must be highlighted that the maximum exerted power, when oxygen mole fraction was higher than 10%, was almost three times higher than that obtained when oxygen mole fraction was 5%. Regarding to the wastewater treatment, a significant decrease in the COD removal was obtained when the MFC performance was reduced due to the limited availability of oxygen, which indicates the significant role of the electrogenic microorganisms in the COD removal in MFC. In addition, the low availability of oxygen at the cathode leads to a lower presence of oxygen at the anode, resulting in an increase in the coulombic efficiency. © 2015 American Institute of Chemical Engineers Biotechnol. Prog., 31:900–907, 2015     

Nitroxide radicals. Controlled release from and transport through biomimetic and hollow fibre membranes

Stable nitroxide radicals have found wide applications in chemistry and biology and they have some potential applications in medicine due to their antioxidant properties. Nitrocellulose filters impregnated with lipid-like substances are used as an imitation of biomembranes and could be used as a controlled drug release vehicle, while experiments with hollow fibres can be useful in the modelling of a drug delivery via blood vessels. This paper describes mechanisms of the nitroxide transport in four different model systems, i.e. a) exit of nitroxide into aqueous solution from porous nitrocellulose filters, impregnated with organic solvents, b) transport of nitroxides through the impregnated membrane from one into another aqueous solution, c) transport of nitroxides from bulk phase of organic solvents through the impregnated membrane into aqueous phase with ascorbic acid, and d) transport of nitroxides from liquid organic phase into aqueous solution through porous hollow fibres. The results are analysed in terms of mass transfer resistance of a membrane, organic and aqueous phase, based on nitroxide diffusion and distribution coefficients. Ascorbic acid reduced nitroxides in water and enhanced the rate of their transfer due to the decrease of transport resistance of unstirred aqueous layers. It is demonstrated that in the case of biomembranes the rate limiting step could be the transport through unstirred aqueous layers and membrane/water interface.     

A kinetic perspective on extracellular electron transfer by anode-respiring bacteria

In microbial fuel cells and electrolysis cells (MXCs), anode-respiring bacteria (ARB) oxidize organic substrates to produce electrical current. In order to develop an electrical current, ARB must transfer electrons to a solid anode through extracellular electron transfer (EET). ARB use various EET mechanisms to transfer electrons to the anode, including direct contact through outer-membrane proteins, diffusion of soluble electron shuttles, and electron transport through solid components of the extracellular biofilm matrix. In this review, we perform a novel kinetic analysis of each EET mechanism by analyzing the results available in the literature. Our goal is to evaluate how well each EET mechanism can produce a high current density (>10 A m⁻²) without a large anode potential loss (less than a few hundred millivolts), which are feasibility goals of MXCs. Direct contact of ARB to the anode cannot achieve high current densities due to the limited number of cells that can come in direct contact with the anode. Slow diffusive flux of electron shuttles at commonly observed concentrations limits current generation and results in high potential losses, as has been observed experimentally. Only electron transport through a solid conductive matrix can explain observations of high current densities and low anode potential losses. Thus, a study of the biological components that create a solid conductive matrix is of critical importance for understanding the function of ARB.     

MEMBRANE POTENTIAL OF THE SQUID GIANT AXON DURING CURRENT FLOW

The squid giant axon was placed in a shallow narrow trough and current was sent in at two electrodes in opposite sides of the trough and out at a third electrode several centimeters away. The potential difference across the membrane was measured between an inside fine capillary electrode with its tip in the axoplasm between the pair of polarizing electrodes, and an outside capillary electrode with its tip flush with the surface of one polarizing electrode. The initial transient was roughly exponential at the anode make and damped oscillatory at the sub-threshold cathode make with the action potential arising from the first maximum when threshold was reached. The constant change of membrane potential, after the initial transient, was measured as a function of the total polarizing current and from these data the membrane potential is obtained as a function of the membrane current density. The absolute value of the resting membrane resistance approached at low polarizing currents is about 23 ohm cm.². This low value is considered to be a result of the puncture of the axon. The membrane was found to be an excellent rectifier with a ratio of about one hundred between the high resistance at the anode and the low resistance at the cathode for the current range investigated. On the assumption that the membrane conductance is a measure of its ion permeability, these experiments show an increase of ion permeability under a cathode and a decrease under an anode.     

TRANSVERSE IMPEDANCE OF THE SQUID GIANT AXON DURING CURRENT FLOW

The change in the transverse impedance of the squid giant axon caused by direct current flow has been measured at frequencies from 1 kc. per second to 500 kc. per second. The impedance change is equivalent to an increase of membrane conductance at the cathode to a maximum value approximately the same as that obtained during activity and a decrease at the anode to a minimum not far from zero. There is no evidence of appreciable membrane capacity change in either case. It then follows that the membrane has the electrical characteristics of a rectifier. Interpreting the membrane conductance as a measure of ion permeability, this permeability is increased at the cathode and decreased at the anode.     

Nitrogen‐Doped Wrinkled Carbon Foils Derived from MOF Nanosheets for Superior Sodium Storage

Preparation of hierarchical carbon nanomaterials from metal?organicframeworks (MOFs) offers immense potential in the improvement of energy density, tunability, and stability of functional materials for energy storage and conversion. How interconnected nitrogen (N)‐doped wrinkled carbon foils derived from MOF nanosheets can serve as high‐performance sodium storage materials due to their multiscale porous structure is shown here. The novel N‐doped carbon nanomaterials are synthesized through the pyrolysis of 2D Mn‐based MOFs, which are produced through the assistance of monodentate ligands to enable the planar growth of MOFs. Subsequent acid etching creates hierarchical pores and channels to allow rapid ion transport. The resulting materials achieve high‐rate capability (165 and 150 mA h g^?1 at current densities of 8 and 10 A g^?1, respectively) and high stability (capacity retention 72.8% after 1000 cycling at 1.0 A g^?1), when they are used as anode in sodium‐ion capacitors.     

Role of nutrient supply on cell growth in bioreactor design for tissue engineering of hematopoietic cells

In the present study, a dynamic mathematical model for the growth of granulocyte progenitor cells in the hematopoietic process is developed based on the principles of diffusion and chemical reaction. This model simulates granulocyte progenitor cell growth and oxygen consumption in a three-dimensional (3-D) perfusion bioreactor. Material balances on cells are coupled to the nutrient balances in 3-D matrices to determine the effects of transport limitations on cell growth. The method of volume averaging is used to formulate the material balances for the cells and the nutrients in the porous matrix containing the cells. All model parameters are obtained from the literature. The maximum cell volume fraction reached when oxygen is depleted in the cell layer at 15 days and is nearly 0.63, corresponding to a cell density of 2.25 x 10(8) cells/mL. The substrate inhibition kinetics for cell growth lead to complex effects with respect to the roles of oxygen concentration and supply by convection and diffusion on cell growth. Variation in the height of the liquid layer above the cell matrix where nutrient supply is introduced affected the relative and absolute amounts of oxygen supply by hydrodynamic flow and by diffusion across a gas permeable FEP membrane. Mass transfer restrictions of the FEP membrane are considerable, and the supply of oxygen by convection is essential to achieve higher levels of cell growth. A maximum growth rate occurs at a specific flow rate. For flow rates higher than this optimal, the high oxygen concentration led to growth inhibition and for lower flow rates growth limitations occur due to insufficient oxygen supply. Because of the nonlinear effects of the autocatalytic substrate inhibition growth kinetics coupled to the convective transport, the rate of growth at this optimal flow rate is higher than that in a corresponding well-mixed reactor where oxygen concentration is set at the maximum indicated by the inhibitory kinetics.     

Conduction-based modeling of the biofilm anode of a microbial fuel cell

The biofilm of a microbial fuel cell (MFC) experiences biofilm-related (growth and mass transport) and electrochemical (electron conduction and charger-transfer) processes. We developed a dynamic, one-dimensional, multi-species model for the biofilm in three steps. First, we formulated the biofilm on the anode as a "biofilm anode" with the following two properties: (1) The biofilm has a conductive solid matrix characterized by the biofilm conductivity (kappa(bio)). (2) The biofilm matrix accepts electrons from biofilm bacteria and conducts the electrons to the anode. Second, we derived the Nernst-Monod expression to describe the rate of electron-donor (ED) oxidation. Third, we linked these components using the principles of mass balance and Ohm's law. We then solved the model to study dual limitation in biofilm by the ED concentration and local potential. Our model illustrates that kappa(bio) strongly influences the ED and current fluxes, the type of limitation in biofilm, and the biomass distribution. A larger kappa(bio) increases the ED and current fluxes, and, consequently, the ED mass-transfer resistance becomes significant. A significant gradient in ED concentration, local potential, or both can develop in the biofilm anode, and the biomass actively respires only where ED concentration and local potential are high. When kappa(bio) is relatively large (i.e., > or =10(-3) mS cm(-1)), active biomass can persist up to tens of micrometers away from the anode. Increases in biofilm thickness and accumulation of inert biomass accentuate dual limitation and reduce the current density. These limitations can be alleviated with increases in the specific detachment rate and biofilm density.     

Increased sustainable electricity generation in up-flow air-cathode microbial fuel cells

Sustainable electricity was generated from glucose in up-flow air-cathode microbial fuel cells (MFCs) with carbon cloth cathode and carbon granular anode. Plastic sieves rather than membrane were used to separate the anode and cathode. Based on 1g/l glucose as substrate, a maximum volumetric power density of 25+/-4 W/m(3) (89 A/m(3)) was obtained for the MFC with a sieve area of 30 cm(2) and 49+/-3 W/m(3) (215 A/m(3)) for the MFC with a sieve area of 60 cm(2). The increased power density with larger sieve area was mainly due to the decrease of internal resistance according to the electrochemistry impedance spectroscopy analysis. Increasing the sieve area from 30 cm(2) to 60 cm(2) resulted in a decrease of overall internal resistance from 41 ohm to 27.5 ohm and a decrease of ohmic resistance from 24.3 ohm to 14 ohm. While increasing operational recirculation ratio (RR) decreased internal resistance and increased power output at low substrate concentration, the effect of RR on cell performance was negligible at higher substrate concentration.     

Optimizing the electrode size and arrangement in a microbial electrolysis cell

This study investigates the influence of anode and cathode size and arrangement on hydrogen production in a membrane-less flat-plate microbial electrolysis cell (MEC). Protein measurements were used to evaluate microbial density in the carbon felt anode. The protein concentration was observed to significantly decrease with the increase in distance from the anode-cathode interface. Cathode placement on both sides of the carbon felt anode was found to increase the current, but also led to increased losses of hydrogen to hydrogenotrophic activity leading to methane production. Overall, the best performance was obtained in the flat-plate MEC with a two-layer 10 mm thick carbon felt anode and a single gas-diffusion cathode sandwiched between the anode and the hydrogen collection compartments.     

Impact of initial biofilm growth on the anode impedance of microbial fuel cells

Electrochemical impedance spectroscopy (EIS) was used to study the behavior of a microbial fuel cell (MFC) during initial biofilm growth in an acetate-fed, two-chamber MFC system with ferricyanide in the cathode. EIS experiments were performed both on the full cell (between cathode and anode) as well as on individual electrodes. The Nyquist plots of the EIS data were fitted with an equivalent electrical circuit to estimate the contributions of various intrinsic resistances to the overall internal MFC impedance. During initial development of the anode biofilm, the anode polarization resistance was found to decrease by over 70% at open circuit and by over 45% at 27 microA/cm(2), and a simultaneous increase in power density by about 120% was observed. The exchange current density for the bio-electrochemical reaction on the anode was estimated to be in the range of 40-60 nA/cm(2) for an immature biofilm after 5 days of closed circuit operation, which increased to around 182 nA/cm(2) after more than 3 weeks of operation and stable performance in an identical parallel system. The polarization resistance of the anode was 30-40 times higher than that of the ferricyanide cathode for the conditions tested, even with an established biofilm. For a two-chamber MFC system with a Nafion 117 membrane and an inter-electrode spacing of 15 cm, the membrane and electrolyte solution dominate the ohmic resistance and contribute to over 95% of the MFC internal impedance. Detailed EIS analyses provide new insights into the dominant kinetic resistance of the anode bio-electrochemical reaction and its influence on the overall power output of the MFC system, even in the high internal resistance system used in this study. These results suggest that new strategies to address this kinetic constraint of the anode bio-electrochemical reactions are needed to complement the reduction of ohmic resistance in modern designs.     

Sodium transport effects on the basolateral membrane in toad urinary bladder

In toad urinary bladder epithelium, inhibition of Na transport with amiloride causes a decrease in the apical (Vmc) and basolateral (Vcs) membrane potentials. In addition to increasing apical membrane resistance (Ra), amiloride also causes an increase in basolateral membrane resistance (Rb), with a time course such that Ra/Rb does not change for 1-2 min. At longer times after amiloride (3-4 min), Ra/Rb rises from its control values to its amiloride steady state values through a secondary decrease in Rb. Analysis of an equivalent electrical circuit of the epithelium shows that the depolarization of Vcs is due to a decrease in basolateral electromotive force (Vb). To see of the changes in Vcs and Rb are correlated with a decrease in Na transport, external current (Ie) was used to clamp Vmc to zero, and the effects of amiloride on the portion of Ie that takes the transcellular pathway were determined. In these studies, Vcs also depolarized, which suggests that the decrease in Vb was due to a decrease in the current output of a rheogenic Na pump. Thus, the basolateral membrane does not behave like an ohmic resistor. In contrast, when transport is inhibited during basolateral membrane voltage clamping, the apical membrane voltage changes are those predicted for a simple, passive (i.e., ohmic) element.     

Adaptation to high current using low external resistances eliminates power overshoot in microbial fuel cells

One form of power overshoot commonly observed with mixed culture microbial fuel cells (MFCs) is doubling back of the power density curve at higher current densities, but the reasons for this type of overshoot have not been well explored. To investigate this, MFCs were acclimated to different external resistances, producing a range of anode potentials and current densities. Power overshoot was observed for reactors acclimated to higher (500 and 5000 Ω) but not lower (5 and 50 Ω) resistances. Acclimation of the high external resistance reactors for a few cycles to low external resistance (5 Ω), and therefore higher current densities, eliminated power overshoot. MFCs initially acclimated to low external resistances exhibited both higher current in cyclic voltammograms (CVs) and higher levels of redox activity over a broader range of anode potentials (-0.4 to 0 V; vs. a Ag/AgCl electrode) based on first derivative cyclic voltammetry (DCV) plots. Reactors acclimated to higher external resistances produced lower current in CVs, exhibited lower redox activity over a narrower anode potential range (-0.4 to -0.2 V vs. Ag/AgCl), and failed to produce higher currents above ～-0.3 V (vs. Ag/AgCl). After the higher resistance reactors were acclimated to the lowest resistance they also exhibited similar CV and DCV profiles. Our findings show that to avoid overshoot, prior to the polarization and power density tests the anode biofilm must adapt to low external resistances to be capable of higher currents.     

Electrokinetic membrane processes in relation to properties excitable tissues. II. Some theoretical considerations

A quantitative theory is presented for the behavior of a membrane-electrolyte system subject to an electric current flow (the "membrane oscillator"). If the membrane is porous, carries "fixed charges," and separates electrolyte solutions of different conductances, it can be the site of repetitive oscillatory changes in the membrane potential, the membrane resistance, and the hydrostatic pressure difference across the membrane. These events are accompanied by a pulsating transport of bulk solutions. The theory assumes the superposition of electrochemical and hydrostatic gradients and centers round the kinetics of resistance changes within the membrane, as caused by effects from diffusion and electro-osmotic fluid streaming. The results are laid down in a set of five simple, basic expressions, which can be transformed into a pair of non-linear differential equations yielding oscillatory solutions. A graphical integration method is also outlined (Appendix II). The agreement between the theory and previous experimental observations is satisfactory. The applied electrokinetic concepts may have importance in relation to analyses of the behavior of living excitable cells or tissues.     

Transport diffusivities of fluids in nanopores by non-equilibrium molecular dynamics simulation

We present a method to study fluid transport through nanoporous materials using highly efficient non-equilibrium molecular dynamics simulations. A steady flow is induced by applying an external field to the fluid particles within a small slab of the simulation cell. The external field generates a density gradient between both sides of the porous material, which in turn triggers a convective flux through the porous medium. The heat dissipated by the fluid flow is released by a Gaussian thermostat applied to the wall particles. This method is effective for studying diffusivities in a slit pore as well as more natural, complex wall geometries. The dependence of the diffusive flux on the external field sheds light on the transport diffusivities and allows a direct calculation of effective diffusivities. Both pore and fluid particle interactions are represented by coarse-grained molecular models in order to present a proof-of-concept and to retain computational efficiency in the simulations. The application of the method is demonstrated in two different scenarios, namely the effective mass transport through a slit pore and the calculation of the effective self-diffusion through this system. The method allows for a distinction between diffusive and convective contributions of the mass transport.     

Effects of vegetation on flow through free water surface wetlands

The one-dimensional Saint-Venant equations are modified to account for stem drag and volumetric displacement effects of dense emergent plants on free surface flow. The modified equations are solved with an implicit finite difference method to give velocities and depths for shallow flows through a vegetated wetland channel. Estimated flow profiles are used to investigate how vegetation density, downstream boundaries and aspect ratio affect detention time, an important parameter in determining nutrient and pollutant removal efficiencies of wetlands constructed to treat wastewater. Results show that free water surface wetlands may exhibit static, neutral or dynamic behavior. Under static conditions, the wetland behaves like a pond in which displacement effects caused by submerged plant mass invariably decrease detention times. Under dynamic conditions, stem drag induced by aquatic plants predominates and wetland detention times increase with vegetation density. These opposing responses are separated by a narrow neutral condition where the presence of vegetation has virtually no net effect on detention time. For a given flow rate and surface area, detention times and hence treatment efficiencies in vegetated free water surface wetlands can be managed to some degree by adjusting the downstream control or by changing the aspect ratio.