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Review Recent progress in electrodes for microbial fuel cells Jincheng Wei, Peng Liang, Xia Huang PII: DOI: Reference: To appear in: Received Date: Revised Date: Accepted Date: S0960-8524(11)00945-X 10.1016/j.biortech.2011.07.019 BITE 8662 Bioresource Technology 10 May 2011 6 July 2011 9 July 2011

Please cite this article as: Wei, J., Liang, P., Huang, X., Recent progress in electrodes for microbial fuel cells, Bioresource Technology (2011), doi: 10.1016/j.biortech.2011.07.019

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Recent progress in electrodes for microbial fuel cells

Jincheng Wei, Peng Liang, Xia Huang* State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing, 100084, P.R. China *Corresponding author: Tel.: +86 10 62772324; Fax: +86 10 62771472; E-mail: xhuang@tsinghua.edu.cn

ABSTRACT 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.

Keywords: microbial fuel cells; electrode materials; electrode configuration; electrode surface modification

1. Introduction Microbial fuel cell (MFC) technology is a prospective technology that purifies wastewater and converts its chemical energy into electrical energy using bacteria as catalysts (Logan et al., 2006). Even with the remarkable improvements in power density, the large-scale application of MFCs has yet to be implemented due to low yields of power generation and high costs. Electrode is the key component in deciding the performance and cost of MFC. Electrode design is the greatest challenge in making MFCs a cost-effective and scalable technology (Rabaey et al., 2009). Recently, interest in the electrode material and its configuration has steadily increased in studies for MFCs. Over the past decade, a variety of electrodes have been extensively explored for MFCs. These electrodes can be classified into two main groups, bio-electrodes (including anode and biocathode) and chemical-electrodes (more specifically, air-cathode and aqueous air-cathode), according to whether or not bacteria is used as a catalyst. The electrode materials in MFC have some general characters and also its self-characteristic. For all the types of electrodes, their base materials must generally be of good conduction, good chemical stability, high mechanical strength, and low cost. Carbon materials and non-corrosive metals, which can basically meet the general

requirements above, are currently the most-widely used base materials (Fig. 1). In addition, there are some specific requirements for each group of electrodes. Bio-electrodes function not only as a conductor, but also as a carrier of bacteria, and some special surface characteristics of electrode materials, such as high surface roughness, good biocompatibility, and efficient electron transfer between bacteria and electrode surface, are essential for high bio-catalytic activity. In order to improve bacterial adhesion and electron transfer, electrode surface modification has become a new topic of interest in the research field of MFCs. The electrode material for air-cathodes with a catalyst is composed of a base material, a catalyst, a binder, and a waterproof coating. Material characteristics and functions are specific for each part. The base material generally only serves as supporting material and current collector. High conductivity and mechanical strength are critical for it. But there is no special requirement for bacteria adhesion. A catalyst is important for air-cathodes, but not absolutely necessary. If necessary, the catalyst is immobilized on the substrate surface with a binder, and a hydrophobic coating is regularly added onto the cathode to avoid water loss. To reduce the cost of air-cathodes, several highly specific materials, such as activated carbon, that do not require a catalyst have been developed and reported (Deng et al., 2010; Zhang et al., 2009a). For aqueous air-cathode, only base material, catalyst and binder are needed. Another great challenge in making MFCs a high performance and scalable technology is electrode configuration. Commonly used electrodes can be classified

according to their configurations: the plane electrode and the three-dimensional electrode. A good configuration for bio-electrodes must provide a large surface area for bacterial adhesion and ensure efficient current collection. Plane electrode is more common for air-electrode. When the air-electrode contains a chemical catalyst, an effective configuration is necessary to ensure the oxygen reduction into a three-phase reaction involving the catalyst, the air, and water (Logan, 2007). In this paper, recent advances in electrode materials and configurations are explored. The advantages and disadvantages of the electrodes are compared in terms of their characteristics, performance, cost, and application range, and the surface modification methods of anode materials are summarized. The microorganisms used in the MFCs studies for anode and biocathode materials were detailed in Tables. Finally, to realize the potential large-scale application of MFCs, the main challenges and directions in electrode development are discussed.

2. Anode materials for MFCs Common materials in laboratory MFCs include a large variety of carbon materials and several metal materials, which vary greatly in configuration and surface area. The configuration and performance of these commonly used anode materials are summarized in Table 1. Photographs of these materials were shown in Fig. 1. It is known that type and concentration of bacteria on anodes is able to significantly affect power density (or current density) in MFCs. Thus the inoculation sources were also

summarized in Table 1. It is shown that mixed culture, including activated sludge, domestic wastewater and preacclimated bacteria from an active MFC (originally inoculated with activated sludge or domestic wastewater), were most common used inoculums in studies for anode materials. However, little research has been done on the effect of inoculation source on power generation and the effect of material characteristics on community structure and biomass. Here, we can loosely think of the difference in inoculation source slightly affected the comparison of anode performance. 2.1. Carbonaceous anode Carbonaceous materials are the most widely used materials for MFC anodes because of their good biocompatibility, good chemical stability, high conductivity, and relatively low cost. In terms of configuration, carbon-based electrodes can be divided into a plane structure, a packed structure, and a brush structure. The carbonaceous electrodes are discussed in detail in this section based on this classification. Plane structure In the laboratory, carbon paper, graphite plates or sheets, and carbon cloth are the most common materials for plain electrodes (Min and Logan, 2004; Sun et al., 2010). Carbon paper is very thin and relatively stiff but slightly brittle. Graphite plates or sheets have higher strength than carbon paper. Roughened graphite electrodes have been reported to produce a higher power density than flat graphite electrodes (ter Heijne et al., 2008). These two materials have a compact structure and a relatively smooth surface, both of which facilitate the quantitative measurement of biomass per unit of surface area. However, their low specific area and high cost inhibit

the application of these electrodes in large-scale MFCs. In comparison with carbon sheets, carbon cloth is more flexible and much more porous, allowing more surface area for bacterial growth. However, it is prohibitively expensive to use for MFCs (ca. $1000/m2) (Zhang et al., 2010). An inexpensive carbon mesh material ($1040/m2) was examined by Wang et al. (2009) as a substantially less expensive alternative to carbon paper and carbon cloth; results showed that the carbon mesh exhibited a slightly higher power density than carbon cloth after both materials were treated with ammonia gas. The comparison of untreated materials, however, was not reported. Besides the plain materials described above, some rarely used fibrous materials, such as graphite foil, carbon fiber veil, and activated carbon cloth, have also been reported and comparatively evaluated for sulfide electrochemical oxidation in the anode of MFCs (Zhao et al., 2008). The results showed that the activated carbon cloth achieved the best sulfide removal and power generation due to its high specific surface and adsorption capacity. Graphite or carbon felt is another fiber fabric that is much thicker than the materials described above. Its loose texture confers more space for bacterial growth than carbon cloth and graphite sheets, but the growth of bacteria is more likely to be restricted by the mass transfer of substrate and products on its inner surface. In order to increase the available surface area for bacteria, the felt is cut into cubes and placed into an anode chamber. Graphite foam is yet another porous carbon-based material with a definite thickness, but it is seldom used in MFCs. Chaudhuri and Lovley (2003) compared the performance of graphite rod, felt, and foam based on the surface area of the resulting

electrode. Similar currents and biomasses were obtained from graphite rod and felt electrodes, and the graphite foam electrode produced 2.4 times more current density and 2.7 times more cell density than the graphite rod one. Several studies on reticulated vitrified carbon (RVC), a significantly porous (97%), conductive (510-3 cm), and rigid but brittle material, as an anode have been conducted (He et al., 2005; Ringeisen et al., 2006; Scott et al., 2008a; Scott et al., 2008b). The specific surface area of RVC was found to be 51 and 6,070 m2/m3 in studies by He et al. (2005) and Ringeisen et al. (2006), respectively. Similar to graphite felt, RVC can be used as packing material with which to fill the anode chamber. Most MFC studies involving the materials mentioned above only focus on maximizing power densities on a volume or membrane area basis, and few studies have reported on normalized power densities at the surface area of the electrode, resulting in difficulties in quantitative comparisons among different materials. More porous anode materials typically produce more power per geometric surface area compared to their smooth counterparts. This is mainly due to the larger surface area available to bacteria per unit volume of anode chamber of porous anode materials. Packed structure To increase the surface area available to bacteria, the use of carbon-based electrodes in packing forms for MFCs anode is becoming increasingly common (Aelterman et al., 2008; Di Lorenzo et al., 2010; Li et al., 2010; Rabaey et al., 2005). Similar to the biological filter, the anode chamber of the MFC can be filled with granular or irregularly shaped packing. However, the granular packing material, such as

granular graphite, must be conductive. Graphite rods are usually used to collect electrons in laboratory-scale MFCs. Having a high specific area is the main advantage of this configuration. The specific area of granular graphite (1.55.5 mm diameter) used in MFCs was estimated to be between 817 and 2,720 m2/m3 (Rabaey et al., 2005). In order to make the complete bed conductive, the granules must be tightly packed next to each other, although dead zones for current collection may still exist after long term running (Logan, 2007). In addition, the porosities of the packed electrode are relatively low (only ranged from 30 to 50% for granular media), and thus, potential clogging after long-term running is another problem (Rabaey et al., 2009). The use of granular graphite as an anode material in packed bed MFCs was first reported by Rabaey et al. (2005). Granular activated carbon (GAC) and small cubes of graphite or carbon felt can also be used as materials for packing bed MFCs. Aelterman et al. (2008) compared graphite and carbon felt, and 2 and 5 mm graphite granules, and found that the graphite felt electrode yielded the highest maximum power output, amounting to up to 386W/m3 in the total anode compartment. Li et al. (2010) reported that a membrane-less MFC, using GAC as the electrode, had a power density 2.5 times higher than an MFC that used carbon cloth. They thus inferred that the high surface area of GAC significantly improves bacterial adhesion and electron transfer from bacteria to the GAC surfaces. Brush structure The graphite brush anode is an ideal electrode that achieves high surface area, high porosities, and efficient current collection. The use of a brush anode was first reported by Logan et al. (2007). In their studies, the brushes were made of

carbon fibers cut to a set length and wound into a twisted core consisting of two conductive but noncorrosive titanium wires. Two brush sizes were used in this study: the smaller brush, about 2.5 cm in diameter and 2.5 cm long, had an estimated surface area of 18,200 m2/m3-brush volume and 95% porosity, while the larger brush, about 5 cm in diameter and 7 cm long, produced 7,170 m2/m3-brush volume and 98% porosity. The cube MFCs containing the smaller brush reached a maximum power density of 2,400 mW/m2 (normalized to the cathode projected surface area), and a maximum Coulombic efficiency (CE) of 60%. Bottle MFCs with the larger brush anode produced a maximum power density of 1,430 mW/m2, versus a 600 mW/m2 plain carbon paper anode. The performance of brushes with different masses of fibers were also tested, but the lack of a clear trend in power per mass loading suggested that the clumping of fibers was a problem that hindered bacterial access to the fiber surfaces, as well as the diffusion of substrate into the brush interior (Logan, 2007). 2.2. Metal and metal oxide anode Metal materials are much more conductive than carbon materials, but they are not widely applicable as carbon materials in MFCs. Many metals were ruled out because of the non-corrosive requirement for anode materials. So far, only stainless steel and titanium have qualified as relative common base materials for anodes. Some of the metal-decorated anodes will be summarized in a later section of this paper. Generally, the smooth surface of metals does not facilitate the adhesion of bacteria. As to be seen in the succeeding sections, some non-corrosive materials, such as stainless

steel, fail to achieve higher power densities compared with carbon materials. Dumas et al. (2007) tested the suitability of a stainless steel plate as both the anode and biocathode electrodes in an MFC, and found that the power density (23 mW/m2) was limited by the anode. In another study, Dumas et al. (2008a) found that the stainless steel anode was less efficient than the graphite one. In contrast, Erable and Bergel (2009) found that the stainless steel grid anode produced much higher current densities than plain graphite ones when a constant potential (-0.1 V vs. the saturated calomel electrode) was applied to them. These results, however, may be reversed when current densities are normalized to the electrode surface. Titanium is another commonly used metal material for MFC anodes. As mentioned above, titanium, such as titanium wires in a graphite brush, is regularly used as a current collector. ter Heijne et al. (2008) compared titanium and graphite in terms of their suitability as an anode in MFCs. Their results showed that the anode performance decreased in the following order: roughened graphite > Pt-coated titanium > flat graphite > uncoated titanium. No current was observed for the uncoated titanium anode. For the three other materials, the specific surface area and biomass activity were important variables in explaining the differences in current density between them. Gold anodes have also been used in several studies (Crittenden et al., 2006; Richter et al., 2008). Richter et al. (2008) found that Geobacter sulfurreducens could grow on gold anodes, producing currents nearly as effectively as in graphite anodes. 2.3. Surface treatments and coatings for the anode materials

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As mentioned above, the surface characteristic of anode materials is one of the deciding factors that affect bacterial attachment and electrical connections between bacteria and the electrode surface. Recently, modification of the anode using different materials, which can be expected to facilitate bacterial adhesion and electron transfer to the anode surface, has been a successful approach for improving power production in studies for MFCs. These modification methods include (i) surface treatments with physical or chemical methods, (ii) addition of highly conductive or electroactive coatings, and (iii) use of metal-graphite composite electrodes are summarized according to their performance improvements on MFC in Table 2. 2.3.1. Surface treatment methods One of the successful surface treatments recorded in earlier reports was achieved by treating a carbon cloth using 5% NH3 gas in a helium carrier gas at 700C, which increased power from 1,640 mW/m2 to 1,970 mW/m2 and reduced the start-up time by 50% (Cheng and Logan, 2007). This improvement due to the increase of the positive surface charge of the cloth from 0.38 to 3.99 meq/m2, and this increase in positive surface charge favor the formation of biofilm. Wang et al. (2009) reported a more environment-friendly and economic method of improving power production in MFCs. This method involved heating the carbon mesh in a muffle furnace at 450 C for 30 min, resulting in a 3% increase in maximum power density. Surface oxidation of carbon materials can also be an effective treatment method. Acid soaking of carbon fiber brushes using concentrated sulfuric acid increased power by 8%, and the combined acid

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and heat anode treatments further increased power by 25% (Feng et al., 2010). The improvement in power generation with the acid and heat treated anode could result from three different factors: (i) Increase in specific area (from 7.11 to 43.9 m2/g) facilitate bacteria adhesion on electrode. (ii) Higher ratio of protonated N to the total N gives more positive charge on electrode surface, which also favors bacteria adhesion. (iii) Lower CO composition on acid and heat treated anode surface may indicate less of contaminants that interfere with charge transfer from bacteria to anode surface (Wang et al. 2009). Lowy and Tender (2008) reported that the kinetic activities of graphite plate anode increased 58.8 times compared to untreated anode through electrochemical oxidation pretreatment at +1.85 V vs. Ag/AgCl. Similarly, Tang et al. (2011) discovered that a graphite felt anode produced 39.5% higher current than an untreated anode after electrochemical oxidization at a constant current density of 30 mA/cm2 for 12 h. The authors thus inferred that electrochemical treatment of graphite felts generates carboxyl-containing functional groups on the surface of the anode. These groups facilitate the electron transfer from bacteria to electrode, due to their strong hydrogen bonding with peptide bonds in bacterial cytochromes. 2.3.2. Coatings Aside from surface treatments, other approaches have been taken to increase anode performance via the addition of a surface coating. The surface coating materials currently reported include carbon nanotubes (CNTs), conductive polymers, mediators,

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metals, and composites of these materials. The most commonly used material is CNT or metal anchored CNT, which has been proven to be efficient for improvements in power generation (Liang et al., 2011; Peng et al., 2010; Sharma et al., 2008; Sun et al., 2010; Tsai et al., 2009; Yuan et al., 2009). Using electrochemical methods, such as cyclic voltammetry and electrochemical impedance spectroscopy, several studies revealed that CNTs can facilitate electron transfer from bacteria to electrode and thus, reduce the internal resistance of MFCs (Peng et al., 2010; Sun et al., 2010). It is known that nanomaterials can inactivate or kill bacteria, thus further investigation of the negative effects of nanomaterials on bacteria metabolism and essential reasons of the promotion in power generation are still needed. The addition of conductive polymers, such as PANI and polypyrrole, to the anode surface has also been tested on MFCs (Jiang and Li, 2009; Zhao et al., 2010). The increase in current densities presumably resulted from the increased surface area and enhanced electron collection of the anode. Supplementary work has also been done on the addition of a CNT/conductive polymer composite to anodes, and the results indicate that the composite coating outperformed CNT/conductive polymers alone (Scott et al., 2007; Zou et al., 2008). In many earlier studies, a variety of mediators, for example, neutral red (NR), anthraquinone-1,6-disulfonic acid (AQDS), and 1,4-naphthoquinone (NQ), were used to facilitate the shuttling of electrons from inside the cell to the electrodes outside the cell. However, all these mediators must be continually added or recycled. This problem can

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be solved by immobilizing the electron mediator on the electrode surface. Mediators immobilized on graphite anodes have been shown to significantly increase power in several studies (Lowy and Tender, 2008; Lowy et al., 2006; Park and Zeikus, 2003; Wang et al., 2011). However, the immobilized mediators could be deactivated due to drop out or degraded during long-term operation. Thus, the stability of this modified electrode needs to be confirmed in practice. Metal and metal oxidation-coated anodes have also been reported in several studies. In microbial electrochemical cells, Fan et al. (2011) decorated graphite with Au nanoparticles. The resulting anode provided current densities 20 times higher than plain graphite were used as anode. Pd-decorated anodes made with similar methods only produced current densities 1.5 to 2.5 times higher than the control. In one study, Kim et al. (2005) reported that iron oxide-coated anodes improved biocompatibility, and thus produced higher power densities and Coulombic efficiency (CE), compared with plain anodes. Similarly, Lowy et al. (2006) found that graphite modified with a graphite paste containing Fe3O4 or Fe3O4 and Ni2+ possessed between 1.52.2 times greater kinetic activity than plain graphite. 2.3.3. Composite electrodes The performance of self-made metal-graphite composite anodes has been tested in several studies. Using an Mn4+-graphite electrode made by mixing manganese sulfate with fine graphite powder, the amount of electrical energy produced can increase 1,000-fold (Park and Zeikus, 2002). Here, Mn4+ was used as a mediator linked to

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graphite electrodes. Lowy et al. (2008) reported that the kinetic activity of an anode made by mixing a sulfide-oxidizing Sb (V) complex and graphite paste was 1.9 times higher than that of a graphite paste anode. The Sb (V) complex usually functioned as a mediator in anode chamber. Thus it can efficiently mediate electron transfer from bacteria to anode. In another study, a graphite-ceramic composite containing Mn2+ and Ni2+ was proven to be kinetically advantageous over plain graphite (Lowy et al., 2006). Whether or not these increases in power are due to the potentials of the metals or other reasons, however, requires further investigation. The studies mentioned above mainly focus on the improvements in power generation performance, but very little is known about the mechanism for these upgrades. As a result, further investigation may be needed to shed light on the mechanism of interactions between bacteria and the electrode surface in order to help advance the knowledge base needed for new anode designs. In addition, the cost-effectiveness of these modified anodes also needs to be evaluated in terms of cost and long-term stability.

3. Cathode materials for MFCs The performance of MFCs is currently limited by the cathode, and this problem is projected to remain for some time (Logan, 2009). Thus, cathode materials and their design are the most challenging aspects of an MFC. Most of the materials mentioned above used as the anode have also been used as the base materials of air-cathodes,

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aqueous air-cathodes, and bio-cathodes (Table 3). The main difference in these materials used for the cathode is that a catalyst (i.e., Pt for oxygen reduction) is normally used but is not always necessary (i.e., ferricyanide) (Logan, 2007). Except for the advances in catalysts, which are not discussed here in detail due to the limited length of this paper, the development of cathode materials is summarized in the following section. 3.1. Air-cathodes and aqueous air-cathodes with catalysts Air-cathodes and aqueous air-cathodes with dissolved oxygen are two of the most commonly used configurations for cathodes for laboratory MFCs that require catalysts. The air-cathodes usually consist of a diffusion layer (exposed to air), a conductive supporting material, and a catalyst/binder layer (exposed to water). Aqueous air-cathodes are made of conductive supporting materials, such as carbon paper, carbon cloth, and platinum mesh, coated with a catalyst/binder layer (Logan et al., 2005; Scott et al., 2008b; Yu et al., 2007). However, the solubility of oxygen (mole fraction basis) in water is only 4.610-6 (25 C) compared to 0.21 in air (Logan, 2007), so the performance of aqueous air-cathodes is limited by their low concentration of dissolved oxygen. Air-cathodes are believed to be a more practical design for MFC cathodes, and they have attracted much more attention than other cathodes because they require no aeration and generate higher power densities. The materials for air-cathodes will be provided in detail in this section. Similar to anode materials, the use of carbon-based electrodes in cloth forms as a supporting material is very common for air-cathodes (Cheng et al., 2006a, b; Logan et

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al., 2007). Compared with carbon paper and carbon cloth, more economical and practical air-cathodes that use stainless steel as the supporting material have been developed by several researchers. Zhang et al. (2010) constructed a cathode around the metal mesh itself, and You et al. (2011) reported the fabrication of a new membrane electrode assembly air-cathode by using stainless steel mesh as a raw material. This cathode achieved a power density similar to an air-cathode based on carbon cloth. When a catalyst is used on a cathode, it is typically bound to the electrode substrate using a polymer. Perfluorosulfonic acid (Nafion) and poly(tetrafluoroethylene) (PTFE) are two commonly used binders in MFCs. Cheng et al., (2006b) compared Nafion and PTFE to determine the effect of these binders on power densities in a single chamber air-cathode MFC. The MFC using Nafion binder produced a higher maximum power density (400 10 ~ 480 20 mW/m2) than that using PTFE (331 3 ~ 360 10 mW/m2). The author gave one possible reason that the biofilm formed on PTFE cathode was thin and loose compared to that formed on Nafion cathode, and biofilm formation is a function of the hydrophobicity of the surface. However, the relation between performance and the inherent properties of binders need to be further investigated. It is worthy of note that Nafion can cost up to 500 times more than PTFE (mass basis) (Cheng et al., 2006b). Further investigations are recommended to identify a new binder with high performance and low cost. To avoid high oxygen fluxes from outside to inside the reactor, as well as water losses through the air-cathode, a hydrophobic coating layer (usually called diffusion

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layer) is needed on the air-facing side of the cathode in a single chamber MFC. Cheng et al. (2006a) found that four PTFE diffusion layers was the optimum number of coatings; this number of coatings resulted to a 171% increase in the CE and a 42% increase in the maximum power density compared with a cathode without diffusion layers. Measurable water loss was prevented as well. Zhang et al. (2010) recently developed an inexpensive coating of poly(dimethylsiloxane) (PDMS) as a diffusion layer for stainless mesh air-cathodes. The CE of the resulting mesh cathodes reached more than 80% and water leakage was prevented. The distance across which proton transfer occurs from a membrane to a cathode is known to be positively correlated with the ohmic resistance of cathode. In order to minimize the internal resistance of air-cathode MFCs, increasing membrane cathode assemblies (MACAs) were developed in recent years. In earlier studies of MACAs (Liu and Logan, 2004; Min and Logan, 2004; Pham et al., 2005), the proton exchange membrane (PEM) was hot pressed to the air-cathode. Kim et al. (2009b) optimized the fabrication conditions for MACAs made by platinum-catalyzed carbon cloth and cation exchange membranes (CEM), and discovered optimal hot-pressing conditions with a temperature of 120 oC and pressure of 150 kg/cm2 for 30 s. Prakash et al. (2010) replaced the ion exchange membrane in MACAs with an inexpensive polyvinylidene fluoride and polystyrene sulfonic acid membrane. Similar maximum power densities were obtained for the two MACAs made with different membranes. Another reported fabrication method is the application of a hydrogel between the ion exchange membrane

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and the carbon cloth air cathode, which increased the cathode potential by about 100 mV over a 05.5 mA range (Kim et al., 2009a). This is because the hydrogel increases the hydration of the cathode and the contact area between the cathode and the membrane. A newly reported fabrication method for MACAs is to coat gas-permeable membranes or fabric with conductive paints and a catalyst. Zuo et al. (2007) developed a tubular MACA by coating a tubular ultrafiltration membrane (UFM) with graphite paint and non-precious metal catalyst. For the MFC reactors with the same volume, this tubular architecture provided much larger surface areas for oxygen reduction, and thus, higher power densities than the plain cathode. Zuo et al. (2008) then replaced UFM with a low-cost anion exchange membrane (AEM) and CEM, and found that the AEM cathode with a conductive coating facing the solution performed better than the CEM and UFM cathode in single-chamber MFCs. Zhuang et al. (2009) constructed a lower cost membrane-less cloth cathode assembly (CCA) by coating a canvas cloth with nickel-based or graphite-based paint and MnO2. Under the fed-batch mode, Ni-CCA and graphite-CCA generated maximum power densities of 86.03 and 24.67 mW/m2 (normalized to the projected cathode surface area) in tubular MFCs, respectively. Despite their comparable performance, such CCAs cost less than 5% of the MACAs mentioned above. 3.2. Air-cathodes and aqueous air-cathodes without catalysts The use of Pt in air-cathodes and aqueous air-cathodes significantly increased the

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cathode cost. The price of cathode materials can account for the greatest percentage (47%) of capital costs of air-cathode MFCs (Rozendal et al., 2008). Many researchers have pursued the possibility of using high specific area carbon materials to reduce the cathodic reaction overpotential, rather than utilizing catalysts. A non-catalyzed aqueous air-cathode made of granular graphite achieved a power output of up to 50 W/m3 (cathode liquid volume) due to the nanoscale pores on it (Freguia et al., 2007). The use of non-catalyzed granular graphite as aqueous air-cathode material was also reported by Tran et al. (2010). Compared with graphite, activated carbon is a more ideal material for non-catalyzed air-cathodes. In the study of Zhang et al. (2009a), activated carbon was cold-pressed with a PTFE binder to form the cathode around a Ni mesh current collector. This air-cathode produced a higher maximum power density (1220 mW/m2, normalized to the cathode projected surface area) than a Pt-catalyzed carbon cloth cathode (1060 mW/m2). Deng et al. (2010) reported the application of an activated carbon fiber felt air-cathode in an up flow MFC; this cathode produced a maximum power density of 315 mW/m2 compared with a platinum-coated carbon paper one, which produced lower values (124 mW/m2, 0.2 mg-Pt/cm2). Electrode modification is another method of increasing the oxygen reduction activity of common carbon materials. In an aqueous air-cathode, Erable et al. (2009) discovered that the use of nitric acid and thermal-activated graphite granules cathode led to a high open circuit voltage of 1,050 mV, which was associated with the increase of material surface and the emergence of nitrogen superficial groups on its surface.

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Air-cathode can also be made with modified carbon materials. Park and Zeikus (2003) fabricated an Fe3+-graphite air-cathode by mixing ferric sulfate with fine graphite powder, kaolin, and nickel chloride. Because Fe3+ can act as electron mediators on the cathode, the Fe3+-graphite cathode showed superior performance compared with a graphite electrode alone. Similarly, Duteanu et al. (2010) compared the oxygen reduction activity of carbon powder modified with various chemicals, including HNO3, H3PO4, KOH, and H2O2, in air-cathode MFCs. The HNO3-treated carbon powder demonstrated the highest current densities (1115 mA/m2, at 5.6 mV), greater than those of a Pt-supported untreated carbon cathode. Overall, activated carbon and HNO3-treated carbon powder achieve higher power generation performance than other materials used in catalyst free air-cathode. And they also outperformed Pt-supported air-cathode. The development of these inexpensive materials significantly increases the cost-performance ratio of air-cathode. 3.3. Biocathode Biocathode have the important advantage of relatively low cost, good stability and multiple functions for wastewater treatment and biosynthesis. Thus it has become a rapidly emerging research topic within the MFC field (Huang et al. 2011). As mentioned above, the same materials are often used for the biocathode and anode in MFCs. Currently, biocathode electrodes are mainly composed of carbon-based materials, such as graphite plate, carbon felt, granular graphite, and graphite fiber brush, as well as stainless steel mesh (Behera et al., 2010; Clauwaert et al., 2007a; Clauwaert et al.,

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2007b; Dumas et al., 2008b; Liang et al., 2009; Xie et al., 2011; You et al., 2009). The surface characteristics and surface area available for bacteria, which depend on the nature of the electrode materials and their configuration, are two main factors that affect the biomass on bio-cathodes and their performance (Huang et al., 2011). Dumas et al. (2008b) reported that stainless steel performed better than graphite in supporting biocathodes when the reactor was inoculated with Geobacter sulfurreducens and the electrodes were polarized at -0.60V vs. Ag/AgCl. De Schamphelaire et al. (2010) found that carbon felt was more suitable than stainless mesh for biocathodes. However, these comparisons of current and power density were not normalized to the surface area of the electrode. Hence, the material more suitable for biocathodes remains unconfirmed. Packed and brush structures are accepted to be superior compared with others because they provide larger surface areas for the configuration of biocathodes. From a cost point of view remains a need for lower-costing electrode materials for practical application.

4. Challenge and outlook The real goal of MFC designs is to achieve practical implementation in a wastewater treatment system. Thus, scale-up is an important issue in MFC design. The main challenges for commercializing scalable MFCs include the development of cost-effective materials and architectures that can be used in larger scale applications. 4.1. Electrode configuration For the anode and bio-cathode of large-scale MFCs, large accessible surface areas

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for bacteria and efficient current collection are essential to achieve high power density. Thus far, packed and brush structures are two relatively ideal configurations that can achieve high surface area for bacterial adhesion. Compared with a packed structure electrode, the high porosities of brush electrodes can effectively avoid the potential for clogging. However, clumping fibers are a potential problem that decreases the effective area of fibers (Logan, 2007). The ohmic resistance of large-scale electrodes is a problem that cannot be neglected. For example the electrical resistivity of graphite is 1,375 cm, compared with only 42 cm for titanium (Rozendal et al., 2008). The resistance is known to be linearly related to the path length of the electron flow. Therefore, the electrical resistivity of carbon materials is relatively high, which can produce high electrode ohmic losses in large-scale systems. In order to decrease the ohmic resistance of large-scale electrodes, a major concern that must be addressed in electrode configuration is the minimization of the travel distance of the electrons that have to flow through electrode materials with low conductivity. Metal current collectors are often used with carbon materials to reduce the overall resistance of the cathode. A good example of such a collector is a graphite fiber brush integrated with a twisted core of titanium wires (Logan et al., 2007). The thickness of the reactor must be reduced and the stainless steel mesh can be used as a current collector for the packed structure electrode. The commonly used carbon-supporting materials for air-cathode can produce high

23

electrode ohmic losses in large-scale systems. Thus, a metal current collector is also necessary. The use of a stainless mesh is helpful in reducing ohmic loss by producing larger air-cathodes (Zhang et al., 2010). The performance of currently used diffusion layers also needs to be further tested for water leakage prevention; these layers could lead to improved CEs under high hydraulic pressure. 4.2. Electrode cost Rozendal et al. (2008) estimated the capital costs of MFCs based on materials currently being used in the laboratory; they showed that the price of cathode materials (air-cathode) can account for the greatest percentage (47%) of MFC capital costs. Thus, reducing the cost of cathode materials is very critical for the practical application of MFCs. An important method of reducing costs is the development of inexpensive base materials, diffusion layer materials, binders, and catalysts. As mentioned above, Zhang et al. (2010) demonstrated that air-cathodes can be constructed using inexpensive metal mesh materials, such as stainless steel, and an inexpensive coating of PDMS. Strong demands for low cost catalysts with non-precious metals, as well as new binders that are less expensive than Nafion, currently exist. Another way of reducing cathode costs is the development of biocathodes. Similar to anodes, packing and brush structures are relatively ideal configurations in terms of practical application. However, based on the electrode materials currently used in the laboratory (i.e., granular graphite, carbon fiber, and metal current collectors), the capital cost of MFCs with biocathodes remains several times more costly than those of conventional wastewater treatment systems. In China,

24

some low cost carbon and metal materials can be obtained from domestic manufacturers (Table 4), but their performance and stability have yet to be tested. On the premise of ensuring a specific level of performance in wastewater treatment and power generation, further development of cost-effective electrode materials is essential for the commercial use of MFCs.

5. Conclusions Electrode designs are the greatest challenge in manufacturing MFCs as a cost-effective technology. A variety of carbon and metal materials have been explored to develop anodes and cathodes, and several electrode modification methods have been developed to improve power generation. The electrode configuration has evolved from a planar to a three-dimensional structure, However, power generation and electrode cost discussed thus far have not reached the levels for commercial use. Further studies on more cost-efficient electrode materials and optimization of configurations are expected to address these challenges and enhance the corporation potential of large-scale MFCs with conventional wastewater treatment systems.

Acknowledgments This research was supported by National High Technology Research and Development Program of China (863 Program) (No. 2009AA06Z306)

25

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characteristics for increasing performance of microbial fuel cells. Environ. Sci. Technol. 43, 8456-8461. Zhao, F., Rahunen, N., Varcoe, J.R., Chandra, A., Avignone-Rossa, C., Thumser, A.E., Slade, R.C.T., 2008. Activated carbon cloth as anode for sulfate removal in a microbial fuel cell. Environ. Sci. Technol. 42, 4971-4976. Zhuang, L., Zhou, S., Wang, Y., Liu, C., Geng, S., 2009. Membrane-less cloth cathode assembly (CCA) for scalable microbial fuel cells. Biosens. Bioelectron. 24, 3652-3656. Zou, Y.J., Xiang, C., Yang, L., Sun, L.X., Xu, F., Cao, Z., 2008. A mediatorless microbial fuel cell using polypyrrole coated carbon nanotubes composite as anode material. Int. J. Hydrogen Energy. 33, 4856-4862. Zuo, Y., Cheng, S.A., Call, D., Logan, B.E., 2007, Tubular membrane cathodes for scalable power generation in microbial fuel cells. Environ. Sci. Technol. 41, 3347-3353. Zuo, Y., Cheng, S.A., Logan, B.E., 2008. Ion exchange membrane cathodes for scalable microbial fuel cells. Environ. Sci. Technol. 42, 6967-6972.

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Figure captions Fig. 1 Photographs of electrode materials used for MFC: (A) carbon paper; (B) graphite plate; (C) carbon cloth; (D) carbon mesh; (E) granular graphite; (F) granular activated carbon; (G) carbon felt; (H) reticulated vitrified carbon; (I) carbon brush; (J) stainless steel mesh.

36

37

Fig. 1 Photographs of electrode materials used for MFC: (A) carbon paper; (B) graphite plate; (C) carbon cloth; (D) carbon mesh; (E) granular graphite; (F) granular activated carbon; (G) carbon felt; (H) reticulated vitrified carbon; (I) carbon brush; (J) stainless steel mesh.

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Table 1 Anode materials, configuration, inoculation source and power generation performance in MFC
Electrode materials Carbon Carbon Carbon Carbon Carbon Carbon Carbon Carbon Carbon Carbon Carbon Carbon Carbon paper Carbon cloth Graphite plate Graphite plate Carbon mesh Activated carbon cloth Granular graphite Graphite felt Carbon felt Granular activated carbon Reticulated vitreous carbon Carbon Configuration Plane Plane Plane Plane Plane Plane Packed Packed Packed Packed Packed Brush Electrode size 2.5 cm 4.5 cm, 22.5 cm2 total 7 cm2 in projected area 1.92 cm2 155 cm2 7 cm2 in projected area 1.5 cm2 in projected area Granular diameters: 1.5~5 mm; anode chamber: 390 mL Anode chamber: 156 mL Anode chamber: 156 mL Anode chamber: 450 mL, wet volume: 250 mL Anode volume: 190 mL; anode surface area: 97 cm2 4 cm long by 3 cm in

Inoculation source
primary clarifier overflow preacclimated bacteria from an active MFC Shewanella oneidensis (MR-1) Shewanella oneidensis (MR-1) preacclimated bacteria from an active MFC D. desulfuricans strain Essex 6 (for sulfate removal) preacclimated bacteria from an active MFC preacclimated bacteria from an active MFC preacclimated bacteria from an active MFC domestic wastewater Anaerobic sludge from a anaerobic bioreactor treating brewery wastewater preacclimated bacteria from

Reactor configuration Two-bottle, air-cathode Single chamber cube air-cathode MFCs Two chamber, air-cathode Two chamber, air-cathode Single chamber air-cathode MFC cube

Maximum power or current density 600 mW/m2 (anode area) 46 W/m3 (anode chamber volume) 3290 mW/m2 (anode area) 1410 mW/m2 (anode area) 893 mW/m2 (anode area), 45 W/m3 (anode chamber volume) 0.51 mW/cm2 (geometric electrode area) 90 W/m3 (net anodic chamber volume) (anode 386 W/m3 chamber volume) (anode 356 W/m3 chamber volume) 5 W/m3 (volume of anode chamber) 170 mW/m2 surface area) (anode

Reference Logan (2007) Zhang (2009b) Dewan (2008) Dewan (2008) Wang (2009) et et al. al.

et al. et al. et al.

Single chamber, air-cathode MFCs Tubular MFC, catholyte: K3Fe(CN)6 Two chamber MFC, catholyte: K3Fe(CN)6 Two chamber MFC, catholyte: K3Fe(CN)6 Single chamber cylindrical MFC, air-cathode Two chamber cylindrical MFC; K3Fe(CN)6 catholyte Single chamber cube

Zhao et al. (2008) Rabaey et al. (2005) Aelterman et al. (2008) Aelterman et al. (2008) Jiang and Li (2009) He et al. (2005) Logan et al.

2400 mW/m2 (cathode

40

Metal Metal

brush Stainless steel plate Pt-coated titanium

Plane Plane

diameter 2030 cm, total surface area 0.12m2 projected area: 22 cm2

an active MFC marine sediments preacclimated bacteria from an active MFC

air-cathode MFC, batch-fed Artificial marine MFC Two chamber (plexiglass plates with flow channels)

area), or 73 W/m3 (anode 23 mW/m2 surface area) unreported

(2007) Dumas et al. (2007) ter Heijne et al. (2008)

41

Table 2 Methods of anode modification, inoculation source and the improvements in performance of MFCs
Materials and methods Surface treatment NH3 gas treatment Surface treatment Surface treatment Surface treatment Surface treatment Surface treatment Surface treatment Surface treatment Surface coating Surface coating Surface coating Surface coating Surface coating Surface coating Surface coating Surface coating Surface coating Surface coating Surface coating Surface coating Surface coating Surface coating Surface coating Composite electrode Heat treatment Heat treatment Acid (H2SO4) treatment Acid (HNO3) treatment Heat and acid treatment Electrochemical oxidation Electrochemical oxidation Carbon nanotube Carbon nanotube Carbon nanotube Polypyrrole coated carbon nanotubes composite Pt decorated carbon nanotube Polyaniline AQDS NQ NR NR Au nanoparticle Pd nanoparticle Iron oxide Graphite paste containing Fe3O4 Graphite paste containing Fe3O4 and Ni2+ Sb(V) complex in graphite paste Base material Carbon clothes Carbon mesh Carbon brush Carbon brush Graphite felt Carbon brush Graphite felt Graphite plates Carbon paper Carbon clothes Glassy carbon Carbon paper Carbon paper Graphite felt Graphite disk Graphite disk Graphite felt Graphite plates Graphite disk Graphite disk Carbon paper Graphite disk Graphite disk Inoculation source domestic wastewater preacclimated bacteria from an active MFC domestic wastewater domestic wastewater brewery wastewater diluted with domestic wastewater (1: 100 by volume) domestic wastewater preacclimated bacteria from an active MFC marine sediments mixed-culture anaerobic granular sludge domestic wastewater Shewanella oneidensis MR-1 Escherichia coli (DH5a strain) Escherichia coli (DH5a strain) brewery wastewater diluted with domestic wastewater (1 : 100 by volume) marine sediments marine sediments Shewanella putrefaciens domestic wastewater Shewanella oneidensis MR-1 Shewanella oneidensis MR-1 anaerobic sludge marine sediments marine sediments marine sediments Improvement in performance Increase power density by 20%, reduce start-up time by 50% Increase power density by 3% Increase power density by 25% Increase power density by 8% 2-fold increase in power density Increase power density by 25% Increase current density by 39.5% 56.8-fold increase in kinetic activities Increase power density by 20% 0.7~30.5-fold increase in power density for different types of reactors 82-fold increase in current density maximum power density 228 mW/m2 ~6-fold increase in the power density 1.8-fold increase in power density 0.7-fold increase in kinetic activity 0.5-fold increase in kinetic activity 54~454-fold increase in current density Power density reached 900 mW/m2 20-fold increase in current density Increase current density by 50~150% 2.75-fold increase in the power density 1.1-fold increase in kinetic activity 0.7-fold increase in kinetic activity 0.9-fold increase in kinetic activity Reference Cheng and Logan (2007) Wang et al. (2009) Feng et al. (2010) Feng et al. (2010) Scott et al. (2007) Feng et al. (2010) Tang et al. (2011) Lowy and Tender (2008) Sun et al. (2010) Tsai et al. (2009) Peng et al. (2010) Zou et al. (2008) Sharma et al. (2008) Scott et al. (2007) Lowy et al. (2006) Lowy et al. (2006) Park and Zeikus (2002) Wang et al. (2010) Fan et al. (2011) Fan et al. (2011) Kim et al. (2005) Lowy et al. (2006) Lowy et al. (2006) Lowy and Tender (2008)

42

Composite electrode Composite electrode

Mn2+ graphite Graphite-ceramic containing Mn2+ and Ni2+

Shewanella putrefaciens marine sediments

78~509 fold increase in current density 1.2-fold increase in kinetic activity

Park and Zeikus (2002) Lowy et al. (2006)

43

Table 3 Cathode materials, configuration and performance in MFC

Type Air-cathode Air-cathode Air-cathode Air-cathode Aqueous air-cathode Air-cathode without catalyst Aqueous air-cathode without catalyst Aqueous air-cathode without catalyst Aqueous air-cathode without catalyst Aqueous air-cathode without catalyst MACA MACA MACA MACA Bio-cathode Cathode materials Carbon clothes, Nafion (binder), no diffusion layer Carbon clothes, PTFE (binder), no diffusion layer Carbon clothes, PTFE (binder), PTFE (diffusion layer) Stainless Steel Mesh, Nafion (binder), poly(dimethylsiloxane) (diffusion layer) Carbon paper Activated carbon was cold-pressed with a PTFE binder around a Ni mesh Granular graphite with nanoscale pores on it Nitric acid and thermal activated graphite granules Activated carbon fiber felt A mixture of ferric sulfate, fine graphite powder, kaolin and nickel chloride PEM carbon clothes cathode assemblies Ultrafiltration (UF) membrane coated with graphite coating and catalyst AEM or CEM coated with graphite coating and catalyst Canvas cloth coated with the mixture of Ni-based (or graphite-based) conductive paints and MnO2 Granular graphite Configuration Plane Plane Plane Plane Plane Plane Packed Packed Plane Plane Plane Tubular Plane Tubular Packed Cathode size 7 cm2 (projected surface area) 7 cm2 (projected surface area) 7 cm2 (projected surface area) 7 cm2 (projected surface area) 2.54.5 cm 7 cm2 (projected surface area) Anode chamber: 350mL, granular diameter <1 mm Anode chamber: 50mL Thickness: 5cm, surface area: 36cm2 20 20 cm
2

Catalyst Pt Pt Pt Pt Pt Pt CoTMPP CoTMPP MnO2

MFC configuration Single chamber cube MFC Single chamber cube MFC Single chamber cube MFC Single chamber cube MFC Two-bottle MFC Single chamber cube MFC Two chamber MFC Cylindrical two chamber MFC Cylindrical two chamber MFC Single chamber MFC Single chamber MFC Single chamber MFC Single chamber MFC Tubular single-chamber MFC Tubular MFC with an internal cathode

Maximum power or current density 400 10 ~ 480 20 mW/m2 (projected area of cathode) 331 3 ~ 360 10 mW/m2 (projected area of cathode) 766 mW/m2 (projected area of cathode) 1610 56 mW/m2 (projected area of cathode) 33 mW/m2 (anode area) 1220 mW/m2 (projected area of cathode) 50 W/m3 (cathode liquid volume) 8.1 W/m (net cathode chamber volume) 315 mW/m2 (cross-sectional area of separator) 788 mW/m2 (surface area of electrode) 262 10 mW/m2 (projected area of cathode) 18 W/m3 (total reactor volume) 449 35 and 286 30 mW/m2 (projected area of cathode) for AEM and CEM, respectively Ni: 86.03 mW/m2; graphite based coating: 24.67 mW/m2 (projected cathode surface area) 8 W/m3 (cathode liquid volume )
3

Reference Cheng et al. (2006b) Cheng et al. (2006b) Cheng et al. (2006a) Zhang et al. (2010) Logan et al. (2005) Zhang et al. (2009) Freguia et al. (2007) Erable et al. (2009) Deng et al. (2010) Park and Zeikus (2003) Liu and Logan (2004) Zuo et al. (2007) Zuo et al. (2008) Zhuang et al. (2010) Clauwaert (2007a) et al.

projected

7 cm (projected surface area) 54 cm (cathode surface area) 7 cm2 (projected surface area) 14.5cm17.5 cm Granular diameters: 1.5~5 mm; cathode chamber: 444 mL
2

Mixture of sediment,

44

aerobic and anaerobic sludge

Bio-cathode Graphite felts (electrochemically pretreated to contain manganese oxide) Tubular Cathode chamber: 40 mL

Mixture of sediment, aerobic and anaerobic sludge

Cylindrical two chamber MFC with a internal anode chamber Two chamber MFC

83 11W/m3 (total MFC volume)

Clauwaert (2007b)

et

al.

Bio-cathode

Graphite fibre brush

Brush

Unreported

Aerobic sludge

68.4 W/m3 (anodic wet volume)

You et al. (2009)

45

Table 4 Cost and estimated bulk density of common electrode materials in MFC Electrode configuration Material Material cost in Chinaa Plane structure Carbon cloth 45~130 (/m2) Packed structure Graphite granule 5.5~20 (/kg) Packed structure Granular activated carbon 0.5~1(/kg) Packed structure Carbon felt 150~300 (/kg) Brush structure Carbon fiber 150~300 (/kg) Plane structure Titanium 100~1000 (/m2) Plane structure Stainless steel mesh 7~50 (/m2) a 2010 values from http://www.alibaba.com/ and http://china.alibaba.com

47

Research Highlights: > The materials of anode and cathode in MFCs are classified according to configuration. > We analyzed the characteristic, performance and cost of these electrode materials. > The modification methods for the anodic electrode are summarized. > The challenges and prospects of future electrode development are briefly discussed.