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Microbial Fuel Cells: Electrode Materials

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DOI: 10.1016/B978-0-12-409547-2.13459-6

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 Microbial Fuel Cells: Electrode Materials
S Kalathil, King Abdullah University of Science and Technology, Thuwal, Saudi Arabia
SA Patil, Technische Universität Braunschweig, Braunschweig, Germany
D Pant, Flemish Institute for Technological Research (VITO), Boeretang, Belgium
ã 2017 Elsevier Inc. All rights reserved.

Microbial Fuel Cells 2

Introduction 2
Current Status 2
Extracellular Electron Transfer Mechanisms Between Microorganisms and Electrodes 3
Interactions of Electrode Materials With Microorganisms 3
Electrode Materials Used in MFCs 4
Anode Materials 4
Carbon-based electrodes 4
Graphite 4
Carbon cloth, felt, mesh, foam, and paper 4
Stainless steel 5
Advanced electrodes 6
Purposely built 3D carbonaceous electrodes 6
Surface modification of 3D electrode materials and 3D composite electrodes 7
Ceramic electrodes 7
Cathode Materials 7
Abiotic cathodes 8
Biotic cathodes (Biocathodes) 8
Summary and Conclusions 8
References 9

Glossary can colonize on the MFC anode and form biofilmsdwidely

Bioanode The electrode where bacteria transfer
metabolically produced electrons after substrate oxidation
reactions and form a biofilm.
Biocathode or biotic cathode The electrode from which
bacteria accept electrons to reduce electron acceptors such as
oxygen.
Electrochemically active bacteria or biofilm Certain
microbes (e.g., Shewanella sp. and Geobacter sp.) are
electrically active and can directly use the anode as a
terminal electron acceptor for achieving their respiration.
These bacteria referred to as electrochemically active bacteria
referred to as electrochemically active biofilms.
Extracellular electron transfer A process in which
electrochemically active bacteria transport their
metabolically generated electrons outside of the cells to
insoluble materials such as anode or metal oxides through a
series of protein networks.
Microbial fuel cell It is a bioelectrochemical system or
device that generates electricity through microbially driven
oxidation of biodegradable substrates at the anode and
abiotic or microbially catalyzed oxygen reduction reaction at
the cathode.

Abbreviations Fe3O4 Magnetite

FeS Ferrous sulfide
3D Three dimensional
ITTC Ice-templated titanium-based ceramics
BES Bioelectrochemical system
LEDs Light-emitting diodes
CaS Calcium sulfide
METs Microbial electrochemical technologies
COD Chemical oxygen demand
MFC Microbial fuel cell
Cu-MF Copper-melamine foam
RVC Reticulated vitreous carbon
EAB Electrochemically active bacteria/biofilm
SEM Scanning electron microscope
EET Extracellular electron transfer
SS Stainless steel
ET Electron transfer

Encyclopedia of Interfacial Chemistry: Surface Science and Electrochemistry http://dx.doi.org/10.1016/B978-0-12-409547-2.13459-6 1

2 Microbial Fuel Cells: Electrode Materials

Microbial Fuel Cells

Introduction
The use of microbial extracellular electron exchange processes for catalyzing oxidation and reduction reactions at electrodes, also
referred to as microbial electrocatalysis, has led to the development of several microbial electrochemical technologies (METs) over
the last decade.1,2 Microbial fuel cells (MFC) are the first and the most widely studied METs and bioelectrochemical systems.
An MFC, like any typical fuel cell, comprises of anodic and cathodic chambers separated by an ion exchange membrane. Whereas
chemical or metallic catalysts facilitate substrate oxidation and reduction reactions in a fuel cell, microorganisms catalyze either of
these or both reactions using electrodes as an electron acceptor or donor source in MFCs. In a two-chambered MFC, microorgan-
isms catalyze substrate oxidation reactions in the anodic compartment and simultaneous chemical and/or microbial substrate
reduction reaction occurs in the cathodic compartment (Fig. 1). Both compartments are usually separated by a proton or cation
exchange membrane and are electrically interconnected through an external circuit with a resistor or load. Anaerobic substrate
oxidation by microorganisms produces carbon dioxide, protons, and electrons. The protons are transferred to the cathode chamber
through a separator. The electrons are transferred first to the anode and then flow to the cathode via an external circuit thereby
producing electricity as the main product. These electrons finally reduce oxygen to produce water as the end product in the cathode
chamber.3
Considering acetate as the electron donor and oxygen as the terminal electron acceptor, the reactions occurring in MFCs can be
shown as below.

Anode : CH3 COOH + 2H2 O ! 2CO2 + 8e + 8H +

Cathode : 2O2 + 8e + 8H + ! 4H2 O
Overall : CH3 COOH + 2O2 ! 2CO2 + 2H2 O + Biomass + Electricity

The ability of MFCs to produce electricity from any biodegradable substrate is potentially being explored for wastewater
treatment applications.4 The MFC technology is attractive not only because of its application in energy harvesting from wastes
but mainly because of its positioning as an eco-friendly alternative or complementary technology to conventional anaerobic
digestion and energy-consuming activated sludge wastewater treatment processes. This is due to its benefits such as low sludge
production, high tolerance to salinity, pH and temperature changes, suitability for low COD containing waste streams, and most
importantly it can help in accomplishing an energy-neutral or energy-positive wastewater treatment process.

Current Status
During the last decade, several scientific and engineering developments due to trans-disciplinary research efforts concerning
fundamental electron transfer mechanisms, reactor configurations, and materials have led to considerable increase in power
generation and wastewater treatment efficiencies of MFCs.4 In addition to wastewater treatment and energy recovery, the
application areas for MFCs have also been expanded to resource recovery of nutrients (e.g., nitrogen and phosphorous)5 and
critical metals,6 biosensing7,8 and desalination.9 Some large-scale practical demonstrations of MFC-based technologies are
currently under trial. Examples include the energy-efficient wastewater treatment system—Electrogenic BioReactor system (www.
emefcy.com), the BioVoltTM reactors for wastewater treatment and energy recovery (http://cambrianinnovation.com/), and the
plant-MFCs powering LEDs (light-emitting diodes) (www.plant-e.com). Lately, the interlinking possibilities of MFCs with other

Fig. 1 A typical two-chambered microbial fuel cell.

 Microbial Fuel Cells: Electrode Materials 3

technologies for the generation of two or more energies and wastewater treatment have also attracted considerable attention.10–12
Despite its sustainable nature and specific application niche, this technology concept still has a long way to go before its full
potential is realized. This is because of scientific and technological challenges such as increasing the power outputs to higher levels
and a considerable decrease in the unit costs since it has to compete in the low-value market.

Extracellular Electron Transfer Mechanisms Between Microorganisms and Electrodes

Electron transfers (ET) are the key components of metabolism and respiration pathways of various life forms, including microor-
ganisms. In order to maximize their energy gain, microbes use the terminal electron acceptor with the highest potential available to
transfer the electrons obtained from the electron donor and accordingly regulate their ET pathways. When there is a limited
availability of the soluble electron acceptors in the environment, they either switch to fermentation metabolism or make use of
insoluble solid electron acceptors.13 In the latter case, microbes transport electrons outside of the cells to achieve the final reduction
reaction via so-called extracellular electron transfer (EET) mechanisms.14 Similarly, microorganisms can also oxidize insoluble
electron donors through EET in soluble electron donor depleted environments. In natural environments, microorganisms use solid
minerals or large organics as electron acceptors or donors. In engineered environments such as MFCs, anode and cathode act as
electron acceptor and donor, respectively. The key mechanisms involved in microbial ET to the anodes that have been identified
and well documented thus far are shown in Fig. 2.15,16
The electrons produced during microbial metabolism can be transferred to the anode via indirect and/or direct ET mechanisms
depending on the microbial catalysts used. In an indirect ET mechanism, ET occurs via self-secreted or exogenous redox mediators
and via the oxidation of reduced primary metabolites such as H2 and formate. In direct ET mechanism, a close physical contact of
the bacterial cell to the anode is necessary. In this case, cellular membrane-spanning (periplasmic and outer-membrane) cyto-
chromes and enzymes, and electrically conductive pili or nanowires facilitate ET to the anode. A few exoelectrogens such as
Geobacter sulfurreducens and Shewanella oneidensis MR-1 use such a direct ET mechanism to communicate electrochemically with the
anodes. Microbes that are not capable of using a direct ET route or are not in physical contact with the anode can utilize the indirect
ET mechanism that is mediated by electron shuttles. Not much is known as far as ET from the cathode to microorganisms is
concerned. Although abiotic air cathodes are preferred or used in most of the MFC studies, O2-reducing microorganisms can also be
used at the cathode to facilitate the oxygen reduction reaction.17 In this case, the cathode is referred to as O2-reducing biocathode.
Based on some studies, it is proposed that similar mechanisms as anodic ET but in reverse direction may exist in biocathodes.
However, importantly, the bacterial components involved in ET at the cathode function at different potentials.17,18

Fig. 2 Electron transfer mechanisms from microorganisms to the anode in microbial fuel cells. (A) Indirect electron transfer via redox mediators and
primary metabolites such as H2, and (B) direct electron transfer via outer-membrane cytochromes, proteins or enzymes, and conductive pili such as
nanowires.

Interactions of Electrode Materials With Microorganisms

The key component of an MFC is the bioanode where microorganisms grow as a biofilm that functions as “living biocatalysts.” The
MFC performance largely depends on this living biofilm, and hence a robust electrochemically active biofilm (EAB) should be
developed at the anode. A prior understanding of microbe–electrode interactions is critical to optimize the anode architectures.
There are several factors affecting the interactions of microbes with the anode such as surface roughness, surface chemistry, material
type, porosity, and hydrophilicity.19 To be a suitable bioanode, the material should meet several criteria as depicted in Fig. 3.
4 Microbial Fuel Cells: Electrode Materials

Fig. 3 Pert diagram showing the criteria for suitable bioanodes. Reproduced from Xie, X.; Criddle, C.; Cui, Y. Design and Fabrication of Bioelectrodes
for Microbial Bioelectrochemical Systems. Energ. Environ. Sci. 2015, 8, 3418–3441 with permission from Royal Society of Chemistry.

Electrode Materials Used in MFCs

Anode Materials
The design of suitable bioanodes is critical to extend the application of MFCs in the real world. The last decade witnessed a
tremendous improvement in the development of highly efficient electrode materials for MFCs.20,21 The most commonly used and
promising anode materials are presented below.

Carbon-based electrodes
Carbon-based electrodes are commonly employed in MFCs due to their biocompatibility, long durability, good conductivity, and
low cost.22 The interesting feature of the carbon material is that it can exhibit various morphologies and structures for designing
attractive and efficient electrodes.22 Carbon-based anodes promote efficient attachment of bacteria by accelerating EAB formation
and provide a conductive pathway for the EET.

Graphite
Graphite is a crystalline form of carbon with the sp2 hybridization structure. Due to high stability and conductivity, graphite is a
promising material as bioelectrodes in MFCs.20 Different forms of graphite electrodes such as rods, felts, foams, and brushes have
been employed as bioanodes in MFCs. For instance, Chaudhuri and Lovley used graphite bioanodes in a glucose-fed MFC using
Rhodoferax ferrireducens as an inoculum.23 The authors observed that the graphite felt bioanode produced higher power density as
compared to the graphite rod. The high surface area of graphite felt led to dense biofilm growth at the bioanode, which allowed
high glucose oxidation. Logan et al. developed graphite brush bioanodes for cubic and bottle air cathode MFCs24 (Fig. 4). The
graphite brush electrode significantly reduced internal resistance of the cubic MFC by producing a power density of 2400 mW/m2.
Graphite sheet-based bioanode outperformed graphite felt in an E. coli-inoculated MFC by producing twofold higher power
density.25 Doping of graphite with metals has been proved to be an effective strategy to improve the bioanode performance. For
example, doping of graphite with calcium sulfide (CaS) enhanced bacterial affinity toward the electrode surface and lowered the
electric potential for the EET process.26 Also, it was noticed that CaS was better dopant over iron-containing compounds, Fe3O4
and FeS.

Carbon cloth, felt, mesh, foam, and paper

Other commonly used carbon materials in MFCs include carbon paper, cloth, mesh and felt. Carbon foam derived from a sponge-
like natural product Pomelo peel generated higher current density over graphite felt and reticulated vitreous carbon (RVC) foam.27
The carbon foam derived from the natural product showed wrinkled surface and high porosity for the efficient biofilm formation
(Fig. 5). Recently, sticky carbon paper electrodes coated with conductive polymers exhibited better bioanode performance than
 Microbial Fuel Cells: Electrode Materials 5

Fig. 4 Graphite fiber brush anode electrode used in (A)-Cubic-MFC (C-MFC) and (B)- Bottle-MFCs (B-MFC), and photographs of the reactors
containing the brush electrodes: (C)- C-MFC shown with the brush anode, and (D)- B-MFC with brush anode and side port cathode. Reproduced from
Logan, B.; Cheng, S.; Watson, V.; Estadt, G. Graphite Fiber Brush Anodes for Increased Power Production in Air-Cathode Microbial Fuel Cells. Environ.
Sci. Technol. 2007, 41, 3341–3346 with permission from American Chemical Society.

carbon felt electrodes by providing large pore size for the bacterial attachment.28 It is known that the virgin forms of carbon cloth
and felt prevent thick biofilm formation at the bioanode due to their hydrophobicity and less porous structures. Hence, the surface
of bioanodes should be pretreated prior to their applications in MFCs for better biofilm formation. Application of a partially
oxidized carbon felt obtained by UV/O3 treatment as the bioanode greatly improved the performance of MFC as compared to
untreated carbon felt through enhanced biofilm formation and ET.29 The partial oxidation of carbon felt created oxygen-containing
functional groups at the bioanode surface that caused an increase in hydrophilicity, a favorable property for bacterial attachment.29
Activation of carbon felt through nitric acid treatment also showed better performance over commercial carbon felt in MFCs.30 The
improved performance of MFC with nitric acid treated bioanode was possibly due to a considerable reduction in the anodic
resistance and increase in surface roughness for bacterial attachment. A simple thermal treatment of carbon mesh and paper can
significantly increase the power generation of MFCs as the heat treatment can remove impurities in the bioanode that obstruct the
conductivity of electrodes.31 A remarkable improvement in the MFC performance was observed by employing plasma-modified
carbon paper as the bioanode.32 The plasma treatment changed the surface properties of carbon paper such as hydrophobicity and
roughness by introducing N+ ions, which, in turn, increased electron transfer to the bioanode. Pretreatment of carbon mesh with
ammonia gas increased the power output of MFCs due to nitrogen doping.31 Liu et al. reported that simple soaking of carbon cloth
in formic acid could boost the performance of bioanode by creating a cleaner surface and reducing oxygen content.33 Similarly,
pretreatment of carbon cloth with hydrogen peroxide, isopropanol, and sodium hypochlorite improved the performance of
MFCs.34
Generally, bacterial cell surfaces are negatively charged and hydrophilic in nature.20 Hence, the introduction of positive charges
and hydrophilicity on the bioanode surface is a good strategy to develop efficient biofilm for better MFC performances. Guo
et al. systematically studied the influence of surface charge and hydrophilicity on the MFC performance by generating various
functional groups on carbon-based bioanodes.35 The study concluded that positively charged bioanodes with hydrophilic nature
showed excellent bioelectrocatalytic performance. In addition, this study provided explanations on why acid, thermal, ammonia,
and plasma pretreatments improved the bioanode performances.

Stainless steel
Stainless steel (SS) is an excellent metal-based material alternative to carbon-based materials as the MFC bioanode due to its
outstanding mechanical properties, electrical conductivity, and corrosion resistance (e.g., of high grade SS materials).36 It is easy to
scale-up and offers stability for long-term operation of MFCs. Recently, several studies have reported SS as efficient bioanodes for
producing stable current densities. A plain SS bioanode outperformed flat graphite electrode by producing higher current under
identical experimental conditions.36 However, the plain SS is not good enough to develop thick and robust biofilm, which may
6 Microbial Fuel Cells: Electrode Materials

Fig. 5 (A), (B), and (C) Scanning electron microscopic (SEM) images of reticulated carbon foam-pomelo peel (RCF-PP) at different magnifications; the
inset of A is a digital image of a peeled Pomelo. (D) Energy dispersive X-ray spectrum of RCF-PP. Reproduced from Chen, S.; Liu, Q.; He, G.
et al. Reticulated Carbon Foam Derived From a Sponge-Like Natural Product as a High Performance Anode in Microbial Fuel Cells. J. Mat. Chem. 2012,
22, 18609–18613 with permission from Royal Society of Chemistry.

prevent to produce high current from the MFC. To tackle this issue, Ketep et al. proposed a three-dimensional (3D) SS foam with
appropriate porosity as the bioanode for MFCs.37 The 3D SS foam produced higher current than plain SS (four times) and carbon
cloth (two times). Surface modification of the SS is also proved to be an effective strategy to improve the performance of SS-based
bioanodes.38 Liang et al. modified the surface of SS by heat treatment, carbon coating, hydrophilization, and polyaniline coating.38
All the surface modifications of SS showed better performance over unmodified plain SS bioanodes that are usually less
biocompatible.

Advanced electrodes
In addition to the use of the traditional materials, researchers have also tried purposely built 3D materials and surface modification
strategies to fabricate anodes for MFCs.

Purposely built 3D carbonaceous electrodes

The production of carbon-based materials at comparatively low costs from biological and chemical polymer precursors via
carbonization (pyrolysis) has led to the development of 3D anodes from synthetic polymers and natural cellulose- and
lignocellulose-containing plant materials. Examples of the first type include carbon fiber-based anodes such as carbon fiber
brushes24 and electrospun carbon fiber mats (maximum current achieved 3 mA/cm2).39 In comparison to the commercial carbon
cloth and felt materials, these materials possessed more organized structures, higher surface area, and better conductivities, which
led to an improved bioelectrocatalytic performance in terms of current or power densities. The carbon fiber brush was fabricated by
winding specific dimension carbon fibers around a twisted core of two titanium wires.24 The mass transfer limitations within the
inner layers and clumping of the fibers were the major issues identified with these carbon brush electrodes. The polyaniline
precursor-based electrospun carbon fiber mats possessed high porosity that allowed efficient mass transfer within the electrode
material but had a low mechanical strength.39
 Microbial Fuel Cells: Electrode Materials 7

The natural precursor materials utilized for purposely built electrodes include loofah,40 kenaf stem (Hibiscus cannabinus),41
coconut shells,42 cardboard,43 mushroom and corn stem,44 and pomelo peel.44 They generally possess macroscale pores that allow
good mass transfer and high specific surface area for biofilm formation. Most of them resulted in achieving higher current densities
(for instance, the multilayered carbonized cardboard anode produced up to 7 mA/cm2) but possessed low mechanical strength and
relatively low conductivity thus limiting their scalability in BESs. Despite several favorable properties of above-mentioned materials
for use as anodes in BESs, some critical limitations such as low conductivity and fragile structures have hindered their large-scale
applications. The lower conductivity of carbon materials, in particular, of the porous electrodes, leads to higher specific electrical
resistivity.

Surface modification of 3D electrode materials and 3D composite electrodes

In order to address the conductivity issue of 3D carbonaceous electrodes, the coating of macroporous scaffolds by conductive
nanoparticles has been tried. For example, the carbon nanoparticles-coated sponge showed good electronic conductivity
( 1 S/cm) and the combination of macroporous sponge structure and microporous nanoparticles layer led to the production of
up to 2.1 mA/cm2 (10.6 mA/cm3 volumetric) current density.45 The metal–polymer hybrid materials such as copper-melamine
foams (Cu-MF) have recently been proposed as 3D anode materials for MFCs.46 These anodes produced up to 2.3  0.6 mA cm2
(volumetric up to 15.5 mA cm3) current density in BESs. This material possesses low gravimetric density, high porosity, high
electric conductivity, and distinct elastic properties that are superior for BES applications. The clogging of 3D structures due to
overgrowth of biofilm that resulted in the decrease in the performance over the longer duration was observed as a critical issue for
the use of such materials.46

Ceramic electrodes
Ceramic-based bioanodes seem to be promising electrode materials for practical applications of MFCs.47 There are many studies
available on ceramic MFCs with outstanding power outputs.47 The ceramics provide a conducive environment for bacterial
attachment and exhibit excellent stability under harsh wastewater conditions. For example, ice-templated titanium-based ceramics
(ITTC) bioanode produced a current density of 128.7 A/m2 in a Geobacter sulfurreducens-based MFC, the highest current density
produced (normalized to the electrode surface area) to date.48 The ITTC provided highly porous 3D architectures and macro-
channels for efficient mass transfer and biofilm formation (Fig. 6).

Cathode Materials
Similar to the bioanode, the cathode is also an integral part of MFCs. Usually, sluggish substrate reduction reactions (mainly
oxygen reduction reaction) at the cathode due to poor catalytic activities of materials mainly limit the performance of MFCs. Hence,

Fig. 6 (A) 3D TiO2 porous scaffold, precursor of ITTC electrodes, (B) SEM image of the internal architecture of the TiO2 scaffold, and (C) ITTC electrode
obtained by reduction of TiO2 porous scaffolds. Arrows indicate the freezing direction. Reproduced from Massazza, D.; Parra, R.; Busalmen, J. P.;
Romeo, H. E.. New Ceramic Electrodes Allow Reaching the Target Current Density in Bioelectrochemical Systems. Energ. Environ. Sci. 2015, 8,
2707–2712 with permission from Royal Society of Chemistry.
8 Microbial Fuel Cells: Electrode Materials

the development of high-performing cathodes has immense priority to improve the performance of MFCs. Most of the electrode
materials used as bioanodes have also been employed for the cathode development. Generally, cathodes are classified as abiotic
and biotic cathodes as summarized below.

Abiotic cathodes
Abiotic cathodes usually reduce oxygen to produce water, which is thermodynamically highly favorable in the presence of a
catalyst. Platinized carbon electrodes are commonly employed as oxygen-reducing cathodes in MFCs.49 However, high cost and
catalyst poisoning prevent the practical applications of Pt-based cathodes. The high-cost Pt has been replaced by other nonprecious
electrodes like Mn2O3, Fe2O3, and heteroatom doped carbon.49,50 The catalyst at the cathode is not needed if ferricyanide is used as
catholyte.51 However, the use of ferricyanide is not sustainable for long-term operation of MFCs.

Biotic cathodes (Biocathodes)

Abiotic cathodes such as Pt add high cost to the large-scale development of MFCs and suffer from poor stability for long-term
operation due to catalytic poisoning. Pt-based abiotic cathodes need a dissolved oxygen concentration of at least 2.2 mg/L in the
catholyte which is 10 times higher than that is needed for aerobic bacteria. Several studies have demonstrated that certain aerobic
bacteria can mimic abiotic cathodes to reduce oxygen to water by forming a biofilm on the cathode.52 The interesting features of
biocathode are self-sustainability and high stability at harsh wastewater conditions. Jang et al. reported that current generation from
an MFC with the biotic cathode increased with time and stabilized after 8 weeks of continuous MFC operation, which was higher
than an abiotic cathode.53 SEM images (Fig. 7) revealed that bacteria attached to the cathode produced nanowires which may be
employed to accept electrons from the cathode. An addition of azide in the catholyte (a known respiratory inhibitor) largely
suppressed the biotic cathode performance while the addition did not have any influence on the abiotic cathode. Kalathil
et al. developed a granular activated carbon (GAC) biocathode for MFC to treat real dye wastewater by reducing oxygen at the
cathode.54–56 The GAC biocathode showed high performance in terms of wastewater treatment, current generation, and stability.
In the absence of oxygen, other chemicals such as nitrate and sulfate can act as electron acceptors at the cathode with denitrifying
bacteria or sulfate-reducing bacteria, respectively.57 The main advantage of anaerobic biocathode over aerobic biocathode is that it
can prevent oxygen diffusion to the anode that can otherwise adversely affect the anodic biofilm.

Summary and Conclusions

Electrodes constitute a major component for MFCs and besides the biocatalyst the most extensively researched area in this field.
Carbon-based materials are most frequently used as electrodes, both anode and cathode. For the anode, the main developments
have been toward the surface treatment to improve the bacterial attachment and biofilm formation. Considerable efforts have also
been directed toward enhancing the specific surface area of the materials for achieving higher anodic biofilm densities. At the
cathode side, oxygen reduction has been the reaction of choice as the electron accepting mechanism, and the efforts here have been
to develop electrodes with non-platinum group metals as catalysts. Over the years, several alternatives have been proposed as
mentioned above for both submerged and gas diffusion air cathodes, which are low-cost and highly performing.58
There is still room for further development of the MFC electrodes as the material science is highly advanced. Highly porous and
conductive materials such as 3D graphene scaffolds are available, which can be employed as both anode and cathode in MFCs.
Electrode materials should be highly stable in harsh wastewater conditions for long-term MFC operation. In particular, 3D
electrode materials should possess optimum pore size to avoid clogging related issues in wastewater treatment applications.
Currently, the high cost of the materials and surface modification strategies mainly hinders the MFC scale-up for practical
applications. Hence, cheaper and stable materials as well as efficient strategies for making composite metal- or carbon-based

Fig. 7 SEM images of the biotic cathodes showing nanowire-like structures. Reproduced from Jang, J. K.; Kan, J.; Bretschger, O.; Gorby, Y. A.; Hsu, L.;
Kim, B. H.; Nealson, K. H. Electricity Generation by Microbial Fuel Cell Using Microorganisms as Catalyst in Cathode. J. Microb. Biotechnol. 2013, 23,
1765–1773 with permission from The Korean Society for Microbiology and Biotechnology.
 Microbial Fuel Cells: Electrode Materials 9

electrodes should be developed to extend the application of MFCs at large-scale levels. Future efforts need to be directed toward
testing upscaling of the efficient electrodes for MFCs as well as making clever combinations of anode and membrane or cathode
and membrane to develop an ideal membrane electrode assembly.

References
1. Schröder, U.; Harnisch, F.; Angenent, L. T. Microbial Electrochemistry and Technology: Terminology and Classification. Energy Environ. Sci. 2015, 8, 513–519.
2. Patil, S. A.; Gildemyn, S.; Pant, D.; Zengler, K.; Logan, B. E.; Rabaey, K. A Logical Data Representation Framework for Electricity-Driven Bioproduction Processes. Biotechnol. Adv.
2015, 33, 736–744.
3. Logan, B. E.; Hamelers, B.; Rozendal, R.; Schröder, U.; Keller, J.; Freguia, S.; Aelterman, P.; Verstraete, W.; Rabaey, K. Microbial Fuel Cells: Methodology and Technology.
Environ. Sci. Tech. 2006, 40, 5181–5192.
4. Pandey, P.; Shinde, V. N.; Deopurkar, R. L.; Kale, S. P.; Patil, S. A.; Pant, D. Recent Advances in the Use of Different Substrates in Microbial Fuel Cells Toward Wastewater
Treatment and Simultaneous Energy Recovery. Appl. Energy 2016, 168, 706–723.
5. Ledezma, P.; Jermakka, J.; Keller, J.; Freguia, S. Recovering Nitrogen as a Solid Without Chemical Dosing: Bio- Electroconcentration for Recovery of Nutrients From Urine.
Environ. Sci. Technol. Lett. 2017, 4, 119–124.
6. Nancharaiah, Y. V.; Mohan, S. V.; Lens, P. N. Biological and Bioelectrochemical Recovery of Critical and Scarce Metals. Trends Biotechnol. 2016, 34, 137–155.
7. Kharkwal, S.; Tan, Y. C.; Lu, M.; Ng, H. Y. Development and Long-Term Stability of a Novel Microbial Fuel Cell bod Sensor With MnO2 Catalyst. Int. J. Mol. Sci. 2017, 18,
276–285.
8. Kretzschmar, J.; Koch, C.; Liebetrau, J.; Mertig, M.; Harnisch, F. Electroactive Biofilms as Sensor for Volatile Fatty Acids: Cross Sensitivity, Response Dynamics, Latency and
Stability. Sens. Actuators B Chem. 2016, 241, 466–472.
9. Sophia, A. C.; Bhalambaal, V. M. Utilization of Coconut Shell Carbon in the Anode Compartment of Microbial Desalination Cell (MDC) for Enhanced Desalination and
Bio-Electricity Production. J. Environ. Chem. Eng. 2015, 3, 2768–2776.
10. Yuan, H.; He, Z. Integrating Membrane Filtration into Bioelectrochemical Systems as Next Generation Energy-Efficient Wastewater Treatment Technologies for Water Reclamation:
A Review. Bioresour. Technol. 2015, 195, 202–209.
11. Dong, Y.; Feng, Y.; Qu, Y.; Du, Y.; Zhou, X.; Liu, J. A Combined System of Microbial Fuel Cell and Intermittently Aerated Biological Filter for Energy Self- Sufficient Wastewater
Treatment. Sci. Rep. 2015, 5, 18070.
12. Tee, P. F.; Abdullah, M. O.; Tan, I. A. W.; Rashid, N. K. A.; Amin, M. A. M.; Nolasco-Hipolito, C.; Bujang, K. Review on Hybrid Energy Systems for Wastewater Treatment and
Bio-Energy Production. Renew. Sustain. Energy Rev. 2016, 54, 235–246.
13. Heijnen, J. J. Bioenergetics of Microbial Growth. In Encyclopedia of Bioprocess Technology; John Wiley & Sons Ltd: Hoboken, NJ, 2002.
14. Shi, L.; Dong, H.; Reguera, G.; Beyenal, H.; Lu, A.; Liu, J.; Yu, H.-Q.; Fredrickson, J. K. Extracellular Electron Transfer Mechanisms Between Microorganisms and Minerals. Nat.
Rev. Microbiol. 2016, 14, 651–662.
15. Kracke, F.; Vassilev, I.; Krömer, J. O. Microbial Electron Transport and Energy Conservation—The Foundation for Optimizing Bioelectrochemical Systems. Front. Microbiol.
2015, 6, 1–18.
16. Patil, S. A.; Hägerhäll, C.; Gorton, L. Electron Transfer Mechanisms Between Microorganisms and Electrodes in Bioelectrochemical Systems. Bioanal. Rev. 2012, 4, 159–192.
17. Erable, B.; Føron, D.; Bergel, A. Microbial Catalysis of the Oxygen Reduction Reaction for Microbial Fuel Cells: A Review. ChemSusChem 2012, 5, 975–987.
18. Rosenbaum, M.; Aulenta, F.; Villano, M.; Angenent, L. T. Cathodes as Electron Donors for Microbial Metabolism: Which Extracellular Electron Transfer Mechanisms Are Involved?
Bioresour. Technol. 2011, 102, 324–333.
19. Xie, X.; Criddle, C.; Cui, Y. Design and Fabrication of Bioelectrodes for Microbial Bioelectrochemical Systems. Energ. Environ. Sci. 2015, 8, 3418–3441.
20. Kalathil, S.; Pant, D. Nanotechnology to Rescue Bacterial Bidirectional Extracellular Electron Transfer in Bioelectrochemical Systems. RSC Adv. 2016, 6, 30582–30597.
21. Kalathil, S.; Nguyen, V. H.; Shim, J.-J.; Khan, M. M.; Lee, J.; Cho, M. H. Enhanced Performance of a Microbial Fuel Cell Using CNT/MnO2 Nanocomposite as a Bionaode Material.
J. Nanosci. Nanotechnol. 2013, 13, 7712–7716.
22. Li, S.; Cheng, C.; Thomas, R. Carbon-Based Microbial-Fuel-Cell Electrodes: From Conductive Supports to Active Catalysts. Adv. Mater. 2017, 29, 1602547.
23. Chaudhuri, S. K.; Lovley, D. R. Electricity Generation by Direct Oxidation of Glucose in Mediatorless Microbial Fuel Cells. Nat. Biotechnol. 2003, 21, 1229–1232.
24. Logan, B.; Cheng, S.; Watson, V.; Estadt, G. Graphite Fiber Brush Anodes for Increased Power Production in Air-Cathode Microbial Fuel Cells. Environ. Sci. Tech. 2007, 41,
3341–3346.
25. Gao, X.; Zhang, Y.; Li, X.; Ye, J. Novel Graphite Sheet Used as an Anodic Material for High-Performance Microbial Fuel Cells. Mat. Lett. 2013, 105, 24–27.
26. Yasri, N. G.; Nakhla, G. Electrochemical Behavior of Anode-Respiring Bacteria on Doped Carbon Electrodes. ACS Appl. Mat. Interf. 2016, 8, 35150–35162.
27. Chen, S.; Liu, Q.; He, G.; et al. Reticulated Carbon Foam Derived from a Sponge-Like Natural Product as a High Performance Anode in Microbial Fuel Cells. J. Mat. Chem. 2012,
22, 18609–18613.
28. Lamberg, P.; Bren, K. L. Extracellular Electron Transfer on Sticky Paper Electrodes: Carbon Paste Paper Anode for Microbial Fuel Cells. ACS Energy Lett. 2016, 1, 895–898.
29. Cornejo, J. A.; Lopez, C.; Babanova, S.; et al. Surface Modification for Enhanced Biofilm Formation and Electron Transport in Shewanella Anodes. J. Electrochem. Soc. 2015,
162, H597–H603.
30. Hidalgo, D.; Tommasi, T.; Bocchini, S.; et al. Surface Modification of Commercial Carbon Felt Used as Anode for Microbial Fuel Cells. Energy 2016, 99, 193–201.
31. Wang, X.; Cheng, S.; Feng, Y.; et al. Use of Carbon Mesh Anodes and the Effect of Different Pretreatment Methods on Power Production in Microbial Fuel Cells. Environ. Sci.
Tech. 2009, 43, 6870–6874.
32. He, Y. R.; Xiao, X.; Li, W.-W.; Sheng, G.-P.; Yan, F.-F.; Yu, H.-Q.; Yuan, H.; Wu, L. J. Enhanced Electricity Production from Microbial Fuel Cells With Plasma-Modified Carbon
Paper Anode. Phys. Chem. Chem. Phys. 2012, 14, 9966–9971.
33. Liu, W.; Cheng, S.; Guo, J. Anode Modification With Formic Acid: A Simple and Effective Method to Improve the Power Generation of Microbial Fuel Cells. Appl. Surf. Sci. 2014,
320, 281–286.
34. Cheng, S.; Liu, W.; Sun, D.; Huang, H. Enhanced Power Production of Microbial Fuel Cells by Reducing the Oxygen and Nitrogen Functional Groups of Carbon Cloth Anode. Surf.
Interf. Anal. 2016. http://dx.doi.org/10.1002/sia.6173.
35. Guo, K.; Freguia, S.; Dennis, P. G.; et al. Effects of Surface Charge and Hydrophobicity on Anodic Biofilm Formation, Community Composition, and Current Generation in
Bioelectrochemical Systems. Environ. Sci. Tech. 2013, 47, 7563–7570.
36. Pocaznoi, D.; Calmet, A.; Etcheverry, L.; Erable, B.; Bergel, A. Stainless Steel is a Promising Electrode for Anodes of Microbial Fuel Cells. Energy Environ. Sci. 2012, 5,
9645–9652.
37. Ketep, S. F.; Bergel, A.; Calmet, A.; Erable, B. Stainless Steel Foam Increases the Current Produced by Microbial Bioanodes in Bioelectrochemical Systems. Energ. Environ. Sci.
2014, 7, 1633–1637.
38. Liang, Y.; Feng, H.; Shen, D.; Li, Na; Guo, K.; et al. Enhancement of Anodic Biofilm Formation and Current Output in Microbial Fuel Cells by Composite Modifications of Stainless
Steel Electrodes. J. Power Sources 2017, 342, 98–104.
39. Chen, S.; Hou, H.; Harnisch, F.; Patil, S. A.; Carmona-Martinez, A. A.; Agarwal, S.; Zhang, Y.; Sinha-Ray, S.; Yarin, A. L.; Greiner, A.; Schröder, U. Electrospun and Solution Blown
Three-Dimensional Carbon Fiber Nonwovens for Application as Electrodes in Microbial Fuel Cells. Energy Environ. Sci. 2011, 4, 1417–1421.
 10 Microbial Fuel Cells: Electrode Materials

40. Yuan, Y.; Zhou, S.; Liu, Y.; Tang, J. Nanostructured Macroporous Bioanode Based on Polyaniline-Modified Natural Loofah Sponge for High-Performance Microbial Fuel Cells.
Environ. Sci. Tech. 2013, 47, 14525–14532.
41. Chen, S.; He, G.; Hu, X.; Xie, M.; Wang, S.; Zeng, D.; Hou, H. A Three-Dimensionally Ordered Macroporous Carbon Derived from a Natural Resource as Anode for Microbial
Bioelectrochemical Systems. ChemSusChem 2012, 5, 1059–1063.
42. Sophia, A. C.; Bhalambaal, V. M. Utilization of Coconut Shell Carbon in the Anode Compartment of Microbial Desalination Cell (MDC) for Enhanced Desalination and
Bio-Electricity Production. J. Environ. Chem. Eng. 2015, 3, 2768–2776.
43. Chen, S.; He, G.; Liu, Q.; Harnisch, F.; Zhou, Y.; Chen, Y.; Hanif, M.; Wang, S.; Peng, X.; Hou, H.; Schroder, U. Layered Corrugated Electrode Macrostructures Boost Microbial
Bioelectrocatalysis. Energy Environ. Sci. 2012, 5, 9769–9772.
44. Karthikeyan, R.; Wang, B.; Xuan, J.; Wong, J. W. C.; Lee, P. K. H.; Leung, M. K. H. Interfacial Electron Transfer and Bioelectrocatalysis of Carbonized Plant Material as Effective
Anode of Microbial Fuel Cell. Electrochim. Acta 2015, 157, 314–323.
45. Xie, X.; Ye, M.; Hu, L.; Liu, N.; McDonough, J. R.; Chen, W.; Alshareef, H. N.; Criddle, C. S.; Cui, Y. Carbon Nanotube-Coated Macroporous Sponge for Microbial Fuel Cell
Electrodes. Energy Environ. Sci. 2012, 5, 5265–5270.
46. Baudler, A.; Langner, M.; Rohr, C.; Greiner, A.; Schröder, U. Metal–Polymer Hybrid Architectures as Novel Anode Platform for Microbial Electrochemical Technologies.
ChemSusChem 2017, 10, 253–257.
47. Winfield, J.; Gajda, I.; Greenman, J.; Ieropoulos, I. A Review Into the Use of Ceramics in Microbial Fuel Cells. Bioresour. Technol. 2016, 215, 296–303.
48. Massazza, D.; Parra, R.; Busalmen, J. P.; Romeo, H. E. New Ceramic Electrodes Allow Reaching the Target Current Density in Bioelectrochemical Systems. Energ. Environ. Sci.
2015, 8, 2707–2712.
49. Zhou, M.; Chi, M.; Luo, J.; He, H.; Jin, T. An Overview of Electrode Materials in Microbial Fuel Cells. J. Power Sources 2011, 196, 4427–4435.
50. Martin, E.; Savadago, O. Cathode Materials Evaluation in Microbial Fuel Cells: A Comparison of Carbon, Mn2O3, Fe2O3 and Platinum Materials. Electrochim. Acta 2011, 58,
58–66.
51. Pant, D.; Singh, A.; Bogaert, G. V.; Olsen, S. I.; Nigam, P. S.; Diels, L.; Vanbroekhoven, K. Bioelectrochemical System (BES) for Sustainable Energy Production and Product
Recovery from Organic Wastes and Industrial Wastewaters. RSC Adv. 2012, 2, 1248–1263.
52. Milner, E. M.; Popescu, D.; Curtis, T.; Head, I. M.; Scott, K.; Yu, E. H. Microbial Fuel Cells With Highly Active Aerobic Biocathodes. J. Power Sources 2016, 324, 8–16.
53. Jang, J. K.; Kan, J.; Bretschger, O.; Gorby, Y. A.; Hsu, L.; Kim, B. H.; Nealson, K. H. Electricity Generation by Microbial Fuel Cell Using Microorganisms as Catalyst in Cathode.
J. Microb. Biotechnol. 2013, 23, 1765–1773.
54. Kalathil, S.; Lee, J.; Cho, M. H. Granular Activated Carbon Based Microbial Fuel Cell for Simultaneous Decolorization of Real Wastewater and Electricity Generation. N. Biotechnol.
2011, 29, 32–37.
55. Kalathil, S.; Lee, J.; Cho, M. H. Efficient Decolorization of Real Dye Wastewater and Bioelectricity Generation Using a Novel Single Chamber Biocathode Microbial Fuel Cell.
Bioresour. Technol. 2012, 119, 22–27.
56. Kalathil, S.; Khan, M. M.; Lee, J.; Cho, M. H. Production of Bioelectricity, Bio-Hydrogen, High Value Chemicals and Bioinspired Nanomaterials by Electrochemically Active
Biofilms. Biotechnol. Adv. 2013, 31, 915–924.
57. He, Z.; Angenent, L. Application of Bacterial Biocathodes in Microbial Fuel Cells. Electroanalysis 2006, 18, 2009–2015.
58. Pant, D.; Van Bogaert, G.; Porto-Carrero, C.; Diels, L.; Vanbroekhoven, K. Anode and Cathode Materials Characterization for a Microbial Fuel Cell in Half Cell Configuration. Water
Sci. Technol. 2011, 63 (10), 2457–2461.

Further Reading
Beyenel, H.; Babauta, J. T. Biofilms in Bioelectrochemical Systems: From Laboratory Practice to Data Interpretation; Wiley & Sons, 2015. ISBN 978-1-118-41349-4.
Guo, K.; Prévoteau, A.; Patil, S. A.; Rabaey, K. Engineering Electrodes for Microbial Electrocatalysis. Curr. Opin. Biotechnol. 2015, 33, 149–156.
Kumar, A.; Hsu, L. H.-H.; Kavanagh, P.; Barrière, F.; Lens, P. N. L.; Lapinsonnière, L.; Lienhard, V.; Schröder, U.; Jiang, S.; Leech, D. The ins and Outs of Microorganism-Electrode
Electron Transfer Reactions. Nat. Rev. Chem. 2017, 1, 1–13.
Logan, B. E. Microbial Fuel Cells; John Wiley & Sons: Hoboken, 2008.
Logan, B. E.; Rabaey, K. Conversion of Wastes Into Bioelectricity and Chemicals by Using Microbial Electrochemical Technologies. Science 2012, 337, 686–690.
Logan, B. E.; Hamelers, B.; Rozendal, R.; Schröder, U.; Keller, J.; Freguia, S.; Aelterman, P.; Verstraete, W.; Rabaey, K. Microbial Fuel Cells: Methodology and Technology. Environ.
Sci. Technol. 2006, 40, 5181–5192.

Relevant Websites
https://www.is-met.org/.
http://www.bioelectrochemical-soc.org/.
http://www.engr.psu.edu/ce/enve/logan/bioenergy/research_mfc.htm.
http://www.geobacter.org/Microbial_Fuel_Cells.
https://www.linkedin.com/groups/1903929.
https://www.mudwatt.com/.

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