Biofouling effects on the performance of microbial fuel cells and recent advances in biotechnological and chemical strategies for mitigation

The occurrence of biofouling in MFC can cause severe problems such as hindering proton transfer and increasing the ohmic and charge transfer resistance of cathodes, which results in a rapid decline in performance of MFC. This is one of the main reasons why scaling-up of MFCs has not yet been successfully accomplished. The present review article is a wide-ranging attempt to provide insights to the biofouling mechanisms on surfaces of MFC, mainly on proton exchange membranes and cathodes, and their effects on performance of MFC based on theoretical and practical evidence. Various biofouling mitigation techniques for membranes are discussed, including preparation of antifouling composite membranes, modification of the physical and chemical properties of existing membranes, and coating with antifouling agents. For cathodes of MFC, use of Ag nanoparticles, Ag-based composite nanoparticles, and antifouling chemicals is outlined in considerable detail. Finally, prospective techniques for mitigation of biofouling are discussed, which have not been given much previous attention in the field of MFC research. This article will help to enhance understanding of the severity of biofouling issues in MFCs and provides up-to-date solutions. It will be beneficial for scientific communities for further strengthening MFC research and will also help in progressing this cutting-edge technology to scale-up, using the most efficient methods as described here.     

Recent advances in the separators for microbial fuel cells

Separator plays an important role in microbial fuel cells (MFCs). Despite of the rapid development of separators in recent years, there are remaining barriers such as proton transfer limitation and oxygen leakage, which increase the internal resistance and decrease the MFC performance, and thus limit the practical application of MFCs. In this review, various separator materials, including cation exchange membrane, anion exchange membrane, bipolar membrane, microfiltration membrane, ultrafiltration membranes, porous fabrics, glass fibers, J-Cloth and salt bridge, are systematically compared. In addition, recent progresses in separator configuration, especially the development of separator electrode assemblies, are summarized. The advances in separator materials and configurations have opened up new promises to overcome these limitations, but challenges remain for the practical application. Here, an outlook for future development and scaling-up of MFC separators is presented and some suggestions are highlighted.     

Proton transfers in the bacteriorhodopsin photocycle

The steps in the mechanism of proton transport in bacteriorhodopsin include examples for most kinds of proton transfer reactions that might occur in a transmembrane pump: proton transfer via a bridging water molecule, coupled protonation/deprotonation of two buried groups separated by a considerable distance, long-range proton migration over a hydrogen-bonded aqueous chain, and capture as well as release of protons at the membrane-water interface. The conceptual and technical advantages of this system have allowed close examination of many of these model reactions, some at an atomic level.     

Proton transfers in the bacteriorhodopsin photocycle

The steps in the mechanism of proton transport in bacteriorhodopsin include examples for most kinds of proton transfer reactions that might occur in a transmembrane pump: proton transfer via a bridging water molecule, coupled protonation/deprotonation of two buried groups separated by a considerable distance, long-range proton migration over a hydrogen-bonded aqueous chain, and capture as well as release of protons at the membrane-water interface. The conceptual and technical advantages of this system have allowed close examination of many of these model reactions, some at an atomic level.     

Development of MFC using sulphonated polyether ether ketone (SPEEK) membrane for electricity generation from waste water

Polyether ether ketone was sulphonated polyether ether ketone (SPEEK) and utilized as a proton exchange membrane (PEM) in a single chamber MFC (SCMFC). The SPEEK was compared with Nafion? 117 in the SCMFC using Escherichia coli. The MFC with the SPEEK membrane produced 55.2% higher power density than Nafion? 117. The oxygen mass transfer coefficient (K(O)) for SPEEK and Nafion? 117 was estimated to be 2.4 × 10(-6)cm/s and 1.6 × 10(-5)cm/s, respectively resulting in reduced substrate loss and increased columbic efficiency (CE) in the case of SPEEK. When the dairy and domestic waste water was treated in SPEEK-SCMFC, fitted with a membrane electrode assembly (MEA), a higher maximum power density was obtained for dairy waste water (5.7 W/m(3)). The results of this study indicate that SPEEK membrane has the potential to greatly enhance the efficiency of MFCs.     

Electricity generation from cellulose by rumen microorganisms in microbial fuel cells

In microbial fuel cells (MFCs) bacteria generate electricity by mediating the oxidation of organic compounds and transferring the resulting electrons to an anode electrode. The objective of this study was to test the possibility of generating electricity with rumen microorganisms as biocatalysts and cellulose as the electron donor in two-compartment MFCs. The anode and cathode chambers were separated by a proton exchange membrane and graphite plates were used as electrodes. The medium in the anode chamber was inoculated with rumen microorganisms, and the catholyte in the cathode compartment was ferricyanide solution. Maximum power density reached 55 mW/m(2) (1.5 mA, 313 mV) with cellulose as the electron donor. Cellulose hydrolysis and electrode reduction were shown to support the production of current. The electrical current was sustained for over 2 months with periodic cellulose addition. Clarified rumen fluid and a soluble carbohydrate mixture, serving as the electron donors, could also sustain power output. Denaturing gradient gel electrophoresis (DGGE) of PCR amplified 16S rRNA genes revealed that the microbial communities differed when different substrates were used in the MFCs. The anode-attached and the suspended consortia were shown to be different within the same MFC. Cloning and sequencing analysis of 16S rRNA genes indicated that the most predominant bacteria in the anode-attached consortia were related to Clostridium spp., while Comamonas spp. abounded in the suspended consortia. The results demonstrated that electricity can be generated from cellulose by exploiting rumen microorganisms as biocatalysts, but both technical and biological optimization is needed to maximize power output.     

A comparison of membranes and enrichment strategies for microbial fuel cells

The external resistance is perhaps the easiest way to influence the operation of a microbial fuel cell (MFC). In this paper, three enrichment strategies, whereby the external resistance was fixed at: (1) a high value in order to maximize the cell voltage (U strategy); (2) a low value in order to maximize the current (I strategy); and (3) a value equal to the internal resistance of the MFC to maximize the power output (P strategy), were investigated. The I strategy resulted in increased maximum power generation and the likely reason is that electron transfer was facilitated under low external resistance, which in turn, favored the development of an electrochemically active biofilm. This experiment was conducted in a single-chamber MFC system equipped with a membrane electrode assembly, and a comparison of the performance achieved by five different membranes is also provided. Selemion was found to be a suitable alternative to Nafion.     

Evaluation of procedures to acclimate a microbial fuel cell for electricity production

A microbial fuel cell (MFC) is a relatively new type of fixed film bioreactor for wastewater treatment, and the most effective methods for inoculation are not well understood. Various techniques to enrich electrochemically active bacteria on an electrode were therefore studied using anaerobic sewage sludge in a two-chambered MFC. With a porous carbon paper anode electrode, 8 mW/m² of power was generated within 50 h with a Coulombic efficiency (CE) of 40%. When an iron oxide-coated electrode was used, the power and the CE reached 30 mW/m² and 80%, respectively. A methanogen inhibitor (2-bromoethanesulfonate) increased the CE to 70%. Bacteria in sludge were enriched by serial transfer using a ferric iron medium, but when this enrichment was used in a MFC the power was lower (2 mW/m²) than that obtained with the original inoculum. By applying biofilm scraped from the anode of a working MFC to a new anode electrode, the maximum power was increased to 40 mW/m². When a second anode was introduced into an operating MFC the acclimation time was not reduced and the total power did not increase. These results suggest that these active inoculating techniques could increase the effectiveness of enrichment, and that start up is most successful when the biofilm is harvested from the anode of an existing MFC and applied to the new anode.     

ESR study of proton transport across phospholipid vesicle membranes

A new method for measuring the rates of proton transfer through bilayer phospholipid membranes using pH-sensitive nitroxyl radicals is suggested. The pH-sensitive alkylating radical was covalently bound to glutathione. This modified glutathione is pH sensitive at pH 1.5-4.5 and does not penetrate across phospholipid membranes. Using ESR this probe was applied to register the kinetics of pH variations inside large unilamellar phospholipid vesicles after creation of a transmembrane proton gradient. In the acidic region (pH approximately 3) the main mechanism of transmembrane proton transfer is that via transport of a proton in the form of an undissociated acid. The membrane permeability coefficients have been determined for a series of acids (HCl, HClO4, HNO3, upper estimate for H2SO4). Taking into account that imidazoline and imidazolidine nitroxyl radicals can be used as pH probes in a wide range of pH, the present method can be developed for measuring the rates of transmembrane proton transfer in neutral and alkaline media.     

Impedance spectroscopy as a tool for non‐intrusive detection of extracellular mediators in microbial fuel cells

Endogenously produced, diffusible redox mediators can act as electron shuttles for bacterial respiration. Accordingly, the mediators also serve a critical role in microbial fuel cells (MFCs), as they assist extracellular electron transfer from the bacteria to the anode serving as the intermediate electron sink. Electrochemical impedance spectroscopy (EIS) may be a valuable tool for evaluating the role of mediators in an operating MFC. EIS offers distinct advantages over some conventional analytical methods for the investigation of MFC systems because EIS can elucidate the electrochemical properties of various charge transfer processes in the bio‐energetic pathway. Preliminary investigations of Shewanella oneidensis DSP10‐based MFCs revealved that even low quantities of extracellular mediators significantly influence the impedance behavior of MFCs. EIS results also suggested that for the model MFC studied, electron transfer from the mediator to the anode may be up to 15 times faster than the electron transfer from bacteria to the mediator. When a simple carbonate membrane separated the anode and cathode chambers, the extracellular mediators were also detected at the cathode, indicating diffusion from the anode under open circuit conditions. The findings demonstrated that EIS can be used as a tool to indicate presence of extracellular redox mediators produced by microorganisms and their participation in extracellular electron shuttling. Biotechnol. Bioeng. 2009; 104: 882–891. © 2009 Wiley Periodicals, Inc.     

Proton translocation by the cytochrome bc1 complexes of phototrophic bacteria: introducing the activated Q-cycle.

The cytochrome bc1 complexes are proton-translocating, dimeric membrane ubiquinol:cytochrome c oxidoreductases that serve as "hubs" in the vast majority of electron transfer chains. After each ubiquinol molecule is oxidized in the catalytic center P at the positively charged membrane side, the two liberated electrons head out, according to the Mitchell's Q-cycle mechanism, to different acceptors. One is taken by the [2Fe-2S] iron-sulfur Rieske protein to be passed further to cytochrome c1. The other electron goes across the membrane, via the low- and high-potential hemes of cytochrome b, to another ubiquinone-binding site N at the opposite membrane side. It has been assumed that two ubiquinol molecules have to be oxidized by center P to yield first a semiquinone in center N and then to reduce this semiquinone to ubiquinol. This review is focused on the operation of cytochrome bc1 complexes in phototrophic purple bacteria. Their membranes provide a unique system where the generation of membrane voltage by light-driven, energy-converting enzymes can be traced via spectral shifts of native carotenoids and correlated with the electron and proton transfer reactions. An "activated Q-cycle" is proposed as a novel mechanism that is consistent with the available experimental data on the electron/proton coupling. Under physiological conditions, the dimeric cytochrome bc1 complex is suggested to be continually primed by prompt oxidation of membrane ubiquinol via center N yielding a bound semiquinone in this center and a reduced, high-potential heme b in the other monomer of the enzyme. Then the oxidation of each ubiquinol molecule in center P is followed by ubiquinol formation in center N, proton translocation and generation of membrane voltage.     

PB/PANI-modified electrode used as a novel oxygen reduction cathode in microbial fuel cell

This study focuses on the preparation of a new type of Prussian Blue/polyaniline (PB/PANI)-modified electrode as oxygen reduction cathode, and its availability in microbial fuel cell (MFC) for biological power generation. The PB/PANI-modified electrode was prepared by electrochemical and chemical methods, both of which exhibited good electrocatalytical reactivity for oxygen reduction in acidic electrolyte. The MFC with PB/PANI-modified cathode aerated by either oxygen or air was shown to yield a maximum power density being the same with that of the MFC with liquid-state ferricyanide cathode, and have an excellent duration as indicated by stable cathode potential for more than eight operating circles. This study suggests a promising potential to utilize this novel electrode as an effective alternative to platinum for oxygen reduction in MFC system without losing sustainability.     

Recent progress in electrodes for microbial fuel cells

The performance and cost of electrodes are the most important aspects in the design of microbial fuel cell (MFC) reactors. A wide range of electrode materials and configurations have been tested and developed in recent years to improve MFC performance and lower material cost. As well, anodic electrode surface modifications have been widely used to improve bacterial adhesion and electron transfer from bacteria to the electrode surface. In this paper, a review of recent advances in electrode material and a configuration of both the anode and cathode in MFCs are provided. The advantages and drawbacks of these electrodes, in terms of their conductivity, surface properties, biocompatibility, and cost are analyzed, and the modification methods for the anodic electrode are summarized. Finally, to achieve improvements and the commercial use of MFCs, the challenges and prospects of future electrode development are briefly discussed.     

石墨烯-多壁碳纳米管复合材料协同刃天青修饰阳极对微生物燃料电池性能的影响

【目的】利用石墨烯与多壁碳纳米管复合材料协同刃天青修饰微生物燃料电池(Microbial fuel cell,MFC)阳极,提高MFC的运行性能。【方法】以碳布为基底,采用滴涂法分别制备了刃天青/碳布(R/CC)、刃天青+石墨烯/碳布(R+GNS/CC)、刃天青+多壁碳纳米管/碳布(R+MWCNT/CC)、刃天青+石墨烯+多壁碳纳米管/碳布(R+GNS+MWCNT/CC)四种阳极材料。【结果】在降解高氯酸盐的过程中,与刃天青/碳布(最高输出电压54 m V)相比,刃天青+石墨烯/碳布、刃天青+多壁碳纳米管/碳布和刃天青+石墨烯+多壁碳纳米管/碳布阳极MFC最高输出电压分别为87、145、275 m V,分别提高了61.11%、168.52%、409.26%;高氯酸盐的还原速率也分别提高了59.1%、89.7%、147.3%。4种阳极的电化学交流阻抗(EIS)和塔菲尔(Tafel)测试发现,与刃天青/碳布阳极相比,刃天青+石墨烯/碳布、刃天青+多壁碳纳米管/碳布阳极活化内阻减小,电极反应速率提高,但刃天青+石墨烯+多壁碳纳米管/碳布阳极的活化内阻更小,电极反应速率更快,同时4种阳极附着微生物胞外聚合物(EPS)分析表明,修饰过的阳极附着微生物数量增加,多糖减少,R+GNS+MWCNT/CC阳极变化最大,更有利于微生物传递电子。【结论】石墨烯、多壁碳纳米管复合材料协同刃天青修饰MFC阳极可以减小活化内阻从而加快电子传递,进而提高MFC的性能。     

Biodegradation and proton exchange using natural rubber in microbial fuel cells

Microbial fuel cells (MFCs) generate electricity from waste but to date the technology’s development and scale-up has been held-up by the need to incorporate expensive materials. A costly but vital component is the ion exchange membrane (IEM) which conducts protons between the anode and cathode electrodes. The current study compares natural rubber as an alternative material to two commercially available IEMs. Initially, the material proved impermeable to protons, but gradually a working voltage was generated that improved with time. After 6 months, MFCs with natural rubber membrane outperformed those with anion exchange membrane (AEM) but cation exchange membrane (CEM) produced 109 % higher power and 16 % higher current. After 11 months, polarisation experiments showed a decline in performance for both commercially available membranes while natural rubber continued to improve and generated 12 % higher power and 54 % higher current than CEM MFC. Scanning electron microscope images revealed distinct structural changes and the formation of micropores in natural latex samples that had been employed as IEM for 9 months. It is proposed that the channels and micropores formed as a result of biodegradation were providing pathways for proton transfer, reflected by the steady increase in power generation over time. These improvements may also be aided by the establishment of biofilms that, in contrast, caused declining performance in the CEM. The research demonstrates for the first time that the biodegradation of a ubiquitous waste material operating as IEM can benefit MFC performance while also improving the reactor’s lifetime compared to commercially available membranes.     

Analysis of ammonia loss mechanisms in microbial fuel cells treating animal wastewater

Ammonia losses during swine wastewater treatment were examined using single- and two-chambered microbial fuel cells (MFCs). Ammonia removal was 60% over 5 days for a single-chamber MFC with the cathode exposed to air (air-cathode), versus 69% over 13 days from the anode chamber in a two-chamber MFC with a ferricyanide catholyte. In both types of systems, ammonia losses were accelerated with electricity generation. For the air-cathode system, our results suggest that nitrogen losses during electricity generation were increased due to ammonia volatilization with conversion of ammonium ion to the more volatile ammonia species as a result of an elevated pH near the cathode (where protons are consumed). This loss mechanism was supported by abiotic tests (applied voltage of 1.1 V). In a two-chamber MFC, nitrogen losses were primarily due to ammonium ion diffusion through the membrane connecting the anode and cathode chambers. This loss was higher with electricity generation as the rate of ammonium transport was increased by charge transfer across the membrane. Ammonia was not found to be used as a substrate for electricity generation, as intermittent ammonia injections did not produce power. The ammonia-oxidizing bacterium Nitrosomonas europaea was found on the cathode electrode of the single-chamber system, supporting evidence of biological nitrification, but anaerobic ammonia-oxidizing bacteria were not detected by molecular analyses. It is concluded that ammonia losses from the anode chamber were driven primarily by physical-chemical factors that are increased with electricity generation, although some losses may occur through biological nitrification and denitrification.     

产电微生物及微生物燃料电池最新研究进展

新型产电微生物(Electricigens)的发现,使得微生物燃料电池概念的内涵发生了根本性的变化,展现了广阔的应用前景。这种微生物能够以电极作为唯一电子受体,把氧化有机物获得的电子通过电子传递链传递到电极产生电流,同时微生物从中获得能量而生长。这种代谢被认为是一种新型微生物呼吸方式。以这种新型微生物呼吸方式为基础的微生物燃料电池可以同时进行废水处理和生物发电,有望可以把废水处理发展成一个有利可图的产业,是MFC最有发展前景的方向。     

The long-term responses of the photosynthetic proton circuit to drought

Proton motive force (pmf) across thylakoid membranes is not only for harnessing solar energy for photosynthetic CO₂ fixation, but also for triggering feedback regulation of photosystem II antenna. The mechanisms for balancing these two roles of the proton circuit under the long-term environmental stress, such as prolonged drought, have been poorly understood. In this study, we report on the response of wild watermelon thylakoid 'proton circuit' to drought stress using both in vivo spectroscopy and molecular analyses of the representative photosynthetic components. Although drought stress led to enhanced proton flux via a ∼34% increase in cyclic electron flow around photosystem I (PS I), an observed ∼fivefold decrease in proton conductivity, g_H⁺, across thylakoid membranes suggested that decreased ATP synthase activity was the major factor for sustaining elevated q_E. Western blotting analyses revealed that ATP synthase content decreased significantly, suggesting that quantitative control of the complex plays a pivotal role in down-regulation of g_H⁺. The expression level of cytochrome b ₆ f complex – another key control point in photosynthesis – also declined, probably to prevent excess-reduction of PS I electron acceptors. We conclude that plant acclimation to long-term environmental stress involves global changes in the photosynthetic proton circuit, in which ATP synthase represents the key control point for regulating the relationship between electron transfer and pmf.     

Bioelectricity production using a new electrode in a microbial fuel cell

Electrode materials play a key role in enhancing the electricity generation in the microbial fuel cell (MFC). In this study, a new material (Ti-TiO(2)) was used as an anode electrode and compared with a graphite electrode for electricity generation. Current densities were 476.6 and 31 mA/m(2) for Ti-TiO(2) and graphite electrodes, respectively. The PCR-DGGE analysis of enriched microbial communities from estuary revealed that MFC reactors were dominated by Shewanella haliotis, Enterococcus sp., and Enterobacter sp. Bioelectrochemical kinetic works in the MFC with Ti-TiO(2) electrode revealed that the parameters by non-linear curve fitting with the confidence bounds of 95% gave good fit with the kinetic constants of η (difference between the anode potential and anode potential giving one-half of the maximum current density) = 0.35 V, K (s) (Half-saturation constant) = 2.93 mM and J (max) = 0.39 A/m(2) for T = 298 K and F = 96.485 C/mol-e(-). From the results observed, it is clear that Ti-TiO(2) electrode is a promising candidate for electricity generation in MFC.     

Air-cathode structure optimization in separator-coupled microbial fuel cells

Microbial fuel cells (MFC) with 30% wet-proofed air cathodes have previously been optimized to have 4 diffusion layers (DLs) in order to limit oxygen transfer into the anode chamber and optimize performance. Newer MFC designs that allow close electrode spacing have a separator that can also reduce oxygen transfer into the anode chamber, and there are many types of carbon wet-proofed materials available. Additional analysis of conditions that optimize performance is therefore needed for separator-coupled MFCs in terms of the number of DLs and the percent of wet proofing used for the cathode. The number of DLs on a 50% wet-proofed carbon cloth cathode significantly affected MFC performance, with the maximum power density decreasing from 1427 to 855 mW/m² for 1–4 DLs. A commonly used cathode (30% wet-proofed, 4 DLs) produced a maximum power density (988 mW/m²) that was 31% less than that produced by the 50% wet-proofed cathode (1 DL). It was shown that the cathode performance with different materials and numbers of DLs was directly related to conditions that increased oxygen transfer. The coulombic efficiency (CE) was more affected by the current density than the oxygen transfer coefficient for the cathode. MFCs with the 50% wet-proofed cathode (2 DLs) had a CE of >84% (6.8 A/m²), which was substantially larger than that previously obtained using carbon cloth air-cathodes lacking separators. These results demonstrate that MFCs constructed with separators should have the minimum number of DLs that prevent water leakage and maximize oxygen transfer to the cathode.