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Microbial Fuel Cell

Microbial Fuel Cell

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Published by Anand Barapatre
Microbial Fuel Cells: Recent Advances, Bacterial Communities and
Application Beyond Electricity Generation
Microbial Fuel Cells: Recent Advances, Bacterial Communities and
Application Beyond Electricity Generation

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Environ. Eng. Res. Vol. 13, No. 2, pp. 51~65, 2008Korean Society of Environmental Engineers
Microbial Fuel Cells: Recent Advances, Bacterial Communities andApplication Beyond Electricity Generation
In S. Kim
, Kyu-Jung Chae, Mi-Jin Choi, and Willy Verstraete
1
 Department of Environmental Science and Engineering, Gwangju Institute of Science and Technology (GIST), 261 Cheomdan-gwagiro, Buk-gu,Gwangju 500-712, South Korea
1
 Laboratory of Microbial Ecology and Technology (LabMET), Faculty of Bioscience Engineering, Ghent University,Coupure Links 653, B-9000 Ghent, Belgium Received April 2008, accepted May 2008
Abstract
The increasing demand for energy in the near future has created strong motivation for environmentally clean alternative energy resources.Microbial fuel cells (MFCs) have opened up new ways of utilizing renewable energy sources. MFCs are devices that convert the chemical energy inthe organic compounds to electrical energy through microbial catalysis at the anode under anaerobic conditions, and the reduction of a terminalelectron acceptor, most preferentially oxygen, at the cathode. Due to the rapid advances in MFC-based technology over the last decade, thecurrently achievable MFC power production has increased by several orders of magnitude, and niche applications have been extended into a varietyof areas. Newly emerging concepts with alternative materials for electrodes and catalysts as well as innovative designs have made MFCs promisingtechnologies. Aerobic bacteria can also be used as cathode catalysts. This is an encouraging finding because not only biofouling on the cathode isunavoidable in the prolonged-run MFCs but also noble catalysts can be substituted with aerobic bacteria. This article discusses some of the recentadvances in MFCs with an emphasis on the performance, materials, microbial community structures and applications beyond electricity generation.
 Keywords
:Bacterial community, Energy, Electricity, Electrochemically active bacteria, Microbial fuel cells
1. Introduction
1
An increasing need for new energy sources due to the con-cerns of the limited availability of fossil fuels has motivated thedevelopment of microbial fuel cells-based technology. After  pioneering studies by groups led by Kim, Zeikus, Lovley andothers, microbial fuel cells (MFCs) have attracted considerableattention over the last decade as a sustainable technology for simultaneous electricity generation and wastewater treatment.Currently, electricity can be generated from any biodegradablecompounds, such as pure chemicals and even wastewater.
1)
The primary mechanisms for electrochemically active microorga-nisms, which are the key biocatalysts involved in electricitygeneration in MFCs, to transfer electrons to the electrodes,metabolic or physiological characteristics, and the fundamen-tals of the anodic or cathodic reactions are well understood.
2)
 As a way of increasing the performance of MFCs, there has
Corresponding author E-mail: iskim@gist.ac.kr Tel: +82-62-970-2436, Fax: +82-62-970-2434
 been considerable work on MFC configurations, their physicaland chemical operating conditions, the choice of microorganisms,and optimization of the microbial metabolism to increase elec-tron donation to the electrodes.
3-9)
As a result, currently achiev-able MFC power production has increased by several orders of magnitude (approximately 10
6
) in less than a decade.
1)
However,many limitations and bottlenecks still need to be overcome inorder to achieve full scale applications. This might be accom- plished with a better understanding of the bacterial communityand dominant anodic species. Community analysis of anodic biofilms enriched in electrochemically active organisms has been carried out by several researchers. These studies showedthat electrochemically active bacteria are widespread in natureand belong to most phyla of bacteria. The bacterial consortiaand predominant species vary with the operational conditions,such as inoculum and substrate type.
1,10-15)
The considerablediversity of bacterial consortia in the anode biofilm suggests the potential existence of other unknown species, beyond the well-known iron reducing bacteria, such as
Geobacter 
and
Shewanella
 species.In recent years, as a result of the rapid advances in MFC re-
 
In S. Kim, Kyu-Jung Chae, Mi-Jin Choi, and Willy Verstraete
52
search, there are several valuable reviews on MFCs reported.These include the following: the microbial metabolism and parameters defining the performance of MFC,
16)
MFC metho-dology and characterizations,
6)
electricity-producing bacterialcommunities,
1)
the characteristics of electrochemically active bacteria in a mediator-less system,
17)
microbial physiology andengineering approaches regarding Benthic Unattended Genera-tors (BUGs) for powering remote sensors,
18)
the primary mecha-nism for electron transfer of electricigens to electrodes,
19)
theadvantages and disadvantages of MFCs compared to the conven-tional anaerobic digestion technology,
20)
the inherent constraintsof MFCs and suggestion for MFC performance improvement,
21)
 the recent advances in MFC configurations and performances,
22)
 and the anodic electron transfer mechanisms in electrochemicallyactive bacteria.
2)
Therefore, this article presents a critical reviewon the advances in MFC with an emphasis on the performancesof MFC, materials, operational factors, microbial communitystructures, and applications beyond electricity generation.
2. MFC Configurations and Designs
In order to increase the power output of MFCs, many studieshave focused on altering their designs to overcome the barriersto electron and proton transport and to enhance the surface areaand reactivity of the electrodes. The essential physical compo-nents of MFCs are the anode, cathode and proton exchangemembrane (PEM, or more precisely a cation exchange memb-rane (CEM)), as shown in Fig. 1. Electrochemically active bac-teria in the anode chamber oxidize the substrate, and separatethe electrons from protons. These electrons and protons travelto the cathode, the former through an external circuit, and thelatter diffusing through the electrolyte and a PEM. The protonsand electrons subsequently combine at the cathode with oxygen,aided by a catalyst such as platinum, to form water.A number of configurations for MFCs have been developed.These are run in batch, fed-bath, or continuous mode, and havea variety of shapes. A two-chambered configuration is a typicalMFC, which consists of an anode and a cathode chamber sepa-rated by a CEM such as Nafion
23,24)
or Ultrex,
25,26)
or even by asalt bridge.
27)
Recently, there has been considerable attention ona single-chambered MFC, which does not require a cathodecompartment because the cathode is exposed directly to air.
7,28)
 Single-chambered MFCs are quite attractive for increasing the power output because they can be run without artificial aerationin an open air cathode systems and can reduce the internal ohmicresistance by avoiding the use of a catholyte as a result of com- bining two chambers. The membrane-less configuration is themost significant advantage of single-chambered MFCs. However,many single-chambered MFCs still use Nafion (or PEM) as a physical separator, where Nafion is either hot-pressed directlyonto the cathode or works as a membrane electrode assembly.
8,12)
 In this case, the use of a catholyte can be avoided but a Nafionmembrane rather is still used. The undesirable back diffusion of oxygen from the cathode to the anode and microbial contamina-tion of the cathode are the two major concerns with single-cham- bered MFCs. A substantial increase in oxygen transfer into theanode chamber in the absence of a PEM was reported.
8)
On theother hand, even with a relatively low power output, two-cham- bered MFCs can have a wide variety of applications. Cathodicdenitrification (nitrate removal as an opportunity for cathodes)or external power assisted biohydrogen production is good ex-ample (explained in detail in a later section). Although memb-rane-less single chambered MFCs could probably be the futureof MFCs due to their elimination of membrane associated pro- blems, there is still considerable room for a two chamberedsystem. Jang et al. (2004) suggested a continuous upflow mem- brane-less MFC, in which the anode is at the bottom and thecathode at the top, with a physical separation by glass wool andglass beads instead of membranes.
3)
In this system the fuel issupplied continuously to the bottom of the anode and the efflu-ent passes through the cathode compartment. This configurationis attractive for wastewater treatment due to its easy scale-upand lack of CEM associated limitations, such as proton transfer  problems.
3,29)
However, oxygen back diffusion is a critical draw- back, which is more severe than in membrane-used MFCs. Re-cently, Clauwaert et al. (2007) demonstrated successful genera-tion of electricity using an open air biocathode system withmicroorganisms that act as biocatalysts for oxygen reductioninstead of chemical catalysts. This is an encouraging finding because noble catalysts can be substituted with aerobic bacteria.
30)
Fig. 1. Conceptual diagram of a microbial fuel cell. This configurationis a typical two-chambered type with an oxygen cathode. The air-bree-ding single chambered system does not require a cathodic chamber. Theelectrons produced from anodic organic oxidation flow through an ex-ternal circuit, whereas the protons are transported through the CEM.The electrons and protons combine with oxygen at the cathode to formwater. The final electron acceptors are as diverse as oxygen, ferricya-nide, hydrogen peroxide, and nitrate. The electrons retrieved from themicrobial oxidation of the substrate are transferred to the anode bydiverse ways such as direct electron transfer from the attached bacteria(1), highly conductive nanowires produced by specific bacteria as along distance transfer (2), and an exogenous mediator or bacterial-originmediator (3). The use of a CEM is optional. S: substrate, CEM: cationexchange membrane, M
Red
: reduced mediator, M
Oxd
: oxidized mediator.
3. Electrode Materials and Catalysts
Currently, finding or choosing the proper materials, such asthe anode, cathode electrodes, and a CEM is one of the critical
 
Microbial Fuel Cells: Recent Advances, Bacterial Communities and Application Beyond Electricity Generation
53
Table 1. Basic components and materials for MFCsComponentsMaterialsRemarksReferencesAnodeStainless steel mesh, graphite plates, rods, granules, carbonfelt, carbon paper, carbon cloth, carbon foam, glassy carbon,Pt, Pt black, reticulated vitreous carbon- Necessary- Must be noncorrosive, conductive, biocompatible, chemically stable, and non-toxic
5, 24, 26, 31, 50, 96-99)
CathodeGraphite, carbon felt, carbon paper, carbon cloth, carbon form,glassy carbon, Pt, Pt black, reticulated vitreous carbon- NecessaryIon exchangemembrane
a
CEM (Nafion, Ultrex), salt bridge, anion exchange membrane- Optional- Permeable to O
2
, ferricyanide, ions, organicmatters (drawbacks)
25, 49, 84)
Electrodecatalyst
 b
Pt, Pt black, MnO
2
, polyaniline, electron mediator immobilizedon anode- Optional- To overcome high overpotential for O
2
reduction
28, 36, 52, 75, 99, 100)
a
Single-chambered systems, such as the air cathode and membrane-less upflow MFC, do not require an ion exchange membrane.
 b
Biocathode system without noble catalyst functions efficiently.
Table 2. Comparison of the power density and Couloumbic efficiency obtained from MFCs with different cathodic catalystsCathode materialCatalystElectron acceptorElectrode surface area (cm
2
)CE (%)
a
PD (W/m
3
)
 b
ReferencesCarbon paperNoneAir11.3 NM0.064
9)
Carbon paperPt (0.5 mg/cm
2
)Air11.363-780.312
9)
Carbon clothCoTMPP (2 mg/cm
2
)Air30NM13.88
c100)
Graphite foilFePc (2 mg/cm
2
)Air30NM14.32
c100)
Graphite foilPyr-FePc (1 mg/cm
2
)
d
Air60NM9.20
51)
Carbon clothNoneAir710-200.093 W/m
2
 
28)e
Carbon clothPt (0.5 mg/cm
2
)+ CoTMPP (0.6 mg/cm
2
)Air77.9-16.30.369 W/m
228)e
Carbon clothCoTMPP (0.5 mg/cm
2
)Air719.70.483 W/m
290)e
Carbon clothFePc-KJB (0.5 mg/cm
2
)
Air728.290.53 W/m
290)e
Carbon clothPt (1 mg/cm
2
)Air719.60.474 W/m
290)e
Graphite granuleNoneAir12606521
36)
a
NM: not mentioned.
 b
Watt per anode volume.
c
Acidified catholyte (pH 3.3) was used.
d
Pyrolyzed FePc.
e
Single-chambered MFC.
FePc on Ketjenblack (KJB) carbon.
challenges for practical applications of MFC. The specific mate-rials for each compartment used in MFCs can affect the power density (PD) and coulombic efficiency (CE). The coulombicefficiency is defined as the ratio of total electrons recovered ascurrent, to maximum possible electrons if all substrate removal produced current. Table 1 gives a summary of the basic compo-nents and materials of MFCs. The materials for the anode elec-trode must be noncorrosive, conducting, biocompatible, andchemically stable in an electrolyte.
6,31)
Carbon felt is a commonelectrode material because it is inexpensive, has a high surfacearea, and is highly conducting but quite fragile. Many studieshave attempted to increase the anode performance by adaptingchemical and physical modification of electrode materials. Itwas reported that the electrical energy produced by MFC wasincreased 1000-fold by adapting a Mn
4+
-graphite anode and aFe
3+
-graphite cathode (788 mW/m
2
) compared with a wovengraphite anode (0.17 mW/m
2
).
32)
A polytetrafluoroaniline or  poly(2-fluoroaniline) modified electrode showed a higher levelof current generation capacity than the unmodified platinumelectrode (530
μ
A/cm
2
for polytetrafluoroaniline, 455
μ
A/cm
2
 for poly(2-fluoroaniline), 11
μ
A/cm
2
for unmodified platinumelectrode).
33,34)
Other modified anodes with anthraquinone-1,6-disulfonic acid (AQDS) or a graphite-ceramic composite con-taining Mn
2+
and Ni
2+
showed 1.7- 2.2 times greater kinetic acti-vity and 5 times greater power density than plain graphite.
35)
 Anode materials modified with inorganic or organic chargetransfer mediators have shown improved kinetics, more rapidtransfer of electrons. Moreover, the addition of a mediator maydirectly reduce the extracytoplasmic electron carriers.In the cathode compartment, expensive catalysts, such as pla-tinum, are generally used to reduce the high overpotential for oxygen reduction.
28)
A plain carbon cathode recorded only amaximum power of 0.02 mW, whereas 0.097 mW was obtainedwith a Pt-coated (0.5 mg/cm
2
) carbon electrode.
9)
Recently, noblemetal-free catalysts, such as pyrolyzed iron phthalocyanine(FePc) or cobalt tetramethoxyphenylporphyrin (CoTMPP), andeven non-catalysts showing comparable performance to a cata-lyzed cathode
36)
have been applied with successful current gene-ration, as summarized in Table 2. Interestingly, aerobic bacteriacan also be used as cathode catalysts, so-called biocathodes.However, there are contradictory reports regarding their effi-ciency.
3,37,38)
Aerobic bacteria respire oxygen at the maximumcapacity in a dissolved oxygen (DO) concentration as low as0.1 mg/L because the terminal oxidases of the aerobic respiratoryelectron transport systems have substantially strong affinity for oxygen.
21)
He and Angenent (2006) showed an increase in the performance of MFC with the development of a biofilm on thecathode.
38)
This is quite encouraging because not only biofou-

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