Sei sulla pagina 1di 10

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
© 2018 Elsevier Inc. All rights reserved.

Microbial Fuel Cells 310


Introduction 310
Current Status 311
Extracellular Electron Transfer Mechanisms Between Microorganisms and Electrodes 311
Interactions of Electrode Materials With Microorganisms 312
Electrode Materials Used in MFCs 312
Anode Materials 312
Carbon-based electrodes 312
Graphite 312
Carbon cloth, felt, mesh, foam, and paper 313
Stainless steel 314
Advanced electrodes 314
Purposely built 3D carbonaceous electrodes 314
Surface modification of 3D electrode materials and 3D composite electrodes 315
Ceramic electrodes 315
Cathode Materials 316
Abiotic cathodes 316
Biotic cathodes (Biocathodes) 316
Summary and Conclusions 316
References 317
Further Reading 318
Relevant Websites 318

Glossary
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 can colonize on the MFC anode and form biofilmsewidely 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
3D Three dimensional
BES Bioelectrochemical system
CaS Calcium sulfide
COD Chemical oxygen demand
Cu-MF Copper-melamine foam
EAB Electrochemically active bacteria/biofilm
EET Extracellular electron transfer
ET Electron transfer
Fe3O4 Magnetite

309
310 Microbial Fuel Cells: Electrode Materials

FeS Ferrous sulfide


ITTC Ice-templated titanium-based ceramics
LEDs Light-emitting diodes
METs Microbial electrochemical technologies
MFC Microbial fuel cell
RVC Reticulated vitreous carbon
SEM Scanning electron microscope
SS Stainless steel

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, microorganisms
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 þ 2H2 O/2CO2 þ 8e þ 8Hþ
Cathode : 2O2 þ 8e þ 8Hþ /4H2 O
Overall : CH3 COOH þ 2O2 /2CO2 þ 2H2 O þ Biomass þ Electricity
The ability of MFCs to produce electricity from any biodegradable substrate is potentially being explored for wastewater treat-
ment 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.

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


Microbial Fuel Cells: Electrode Materials 311

Current Status
During the last decade, several scientific and engineering developments due to trans-disciplinary research efforts concerning funda-
mental 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 bio-
sensing7,8 and desalination.9 Some large-scale practical demonstrations of MFC-based technologies are currently under trial. Exam-
ples include the energy-efficient wastewater treatment systemdElectrogenic 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 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 avail-
ability 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 mecha-
nisms 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) cytochromes and enzymes, and electrically conductive pili or nanowires facilitate ET to the anode. A few exoe-
lectrogens such as Geobacter sulfurreducens and Shewanella oneidensis MR-1 use such a direct ET mechanism to communicate elec-
trochemically 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.
312 Microbial Fuel Cells: Electrode Materials

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.

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 tremen-
dous improvement in the development of highly efficient electrode materials for MFCs.20,21 The most commonly used and prom-
ising 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

Fig. 3 Pert diagram showing the criteria for suitable bioanodes. Reproduced from Xie, X.; Criddle, C.; Cui, Y. Design and Fabrication of Bio-
electrodes for Microbial Bioelectrochemical Systems. Energ. Environ. Sci. 2015, 8, 3418–3441 with permission from Royal Society of Chemistry.
Microbial Fuel Cells: Electrode Materials 313

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 con-
taining 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.

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
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 Nþ 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.
314 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.

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
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
Microbial Fuel Cells: Electrode Materials 315

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
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 nano-
particles has been tried. For example, the carbon nanoparticles-coated sponge showed good electronic conductivity (z1 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 cm 2 (volumetric up to
15.5 mA cm 3) 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 attach-
ment 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 macrochannels for effi-
cient mass transfer and biofilm formation (Fig. 6).

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 elec-
trode 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.
316 Microbial Fuel Cells: Electrode Materials

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, the
development of high-performing cathodes has immense priority to improve the performance of MFCs. Most of the electrode mate-
rials 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 elec-
trodes 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 oper-
ation due to catalytic poisoning. Pt-based abiotic cathodes need a dissolved oxygen concentration of at least 2.2 mg/L in the cath-
olyte 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.

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 317

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

See also: Enzymatic Electrodes: Characteristics, Fabrication Methods, and Applications; Enzymatic Phosphorylation of Peptides and Proteins;
Implantable Enzyme-Based Biofuel Cells.

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 ConservationdThe 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. https://doi.org/10.1002/sia.6173.
318 Microbial Fuel Cells: Electrode Materials

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.
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/.

Potrebbero piacerti anche