Arabian Journal of Chemistry (2015) xxx, xxx–xxx

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

Electron transfer mechanisms, characteristics

and applications of biological cathode microbial
fuel cells – A mini review
a,*
Hai-Liang Song , Ying Zhu b, Jie Li a

a
School of Energy and Environment, Southeast University, Nanjing 210096, China
b
Faculty of Civil Engineering, The University of Hong Kong, Pokfulam, Hong Kong

Received 10 July 2013; accepted 14 January 2015

KEYWORDS Abstract Since the microbial fuel cells (MFCs) research in the laboratory has reached an unprece-
Microbial fuel cell; dented success, it has raised a research upsurge internationally in recent years. However, compared
Bio-cathode; with laboratory studies, the widespread applications of the conventional MFCs were restrained by
Final electron acceptor; the limitations of high cost and low efficiency. This stimulates researchers to overcome the obsta-
Wastewater treatment; cles. In this condition, bio-cathodes attracted their great interests. This paper is a brief review about
Biosensors the experimental progress of bio-cathodes in microbial fuel cells with an emphasis on the classifica-
tion according to the final electron acceptors and the comparison with the traditional abiotic cath-
ode MFCs. Bio-cathodes are feasible in removing nutrient in wastewater treatment and being used
as biosensors in bioremediation. Presently, tremendous efforts are being made in investigating
appropriate electrodes and dominant strains to achieve the effective practical applications.
ª 2015 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University. This is
an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2. Classifications of bio-cathodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.1. Oxygen as the terminal electron acceptor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.1.1. Oxygen as a direct electron acceptor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

* Corresponding author.
E-mail address: songhailiang@seu.edu.cn (H.-L. Song).
Peer review under responsibility of King Saud University.

Production and hosting by Elsevier

http://dx.doi.org/10.1016/j.arabjc.2015.01.008
1878-5352 ª 2015 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Please cite this article in press as: Song, H.-L. et al., Electron transfer mechanisms, characteristics and applications of biological cathode microbial fuel cells – A mini
review. Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.01.008
2 H.-L. Song et al.

2.1.2. Oxygen as an indirect electron acceptor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

2.2. Inorganic salts as the electron acceptor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.3. Others . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3. Advantages and disadvantages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.1. Advantages of bio-cathode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.1.1. Lower expense . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.1.2. Improved sustainability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.1.3. Easy improvement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.2. Disadvantages of bio-cathode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.2.1. Fluctuation of pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.2.2. Material of cathode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.2.3. Others . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
5. Prospect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

1. Introduction Aneenent, 2006). This review aims at classifying the types of

After being stricken by energy crises, people have realized the
urgency to change the energy structure, which depends too
strongly on fossil fuels. Some renewable and sustainable
resources are proposed to alleviate the situation, among which
bioenergy is considered as the most efficient way. Inspired by
Luigi Galvani (1737–1798), an Italian physician and also a
physicist, found that frogs tissues are endowed with an intrin-
sic electricity, which proved the existence of animal electricity
(Piccolino, 1998). Michael C. Potter established the first micro-
bial fuel cell (MFC) in 1911, and he demonstrated a current
flow between two electrodes emerged in a bacterial culture
and in sterile medium (He and Aneenent, 2006). The current
design concept of MFC came into existence in 1977 with the
work by Karube et al. (1977). However, little was known about
how MFCs fecundated at that time. In 1999, Kim et al. suc-
cessfully found electricity generation uses MFCs, which were
regarded as a milestone of the development of MFCs (Kim
et al., 1999).
Consisting of an anode chamber and a cathode chamber,
which are separated by the proton exchange membranes, a
MFC’s power can be generated from the oxidation of organic
matter by bacteria at the anode, with reduction of oxygen at
the cathode (Logan et al., 2005). According to numerous find-
ings, the configurations of MFCs are quite various, including
air–cathode MFCs, aqueous cathodes using dissolved oxygen,
and two-chamber reactors with soluble catholytes or poised
potentials, tubular packed bed reactors and so on. In these dif-
ferent configurations of MFCs, microbes only exist in the
anode chamber. However, some investigations found that bac-
teria grew quite inevitably in the cathodes and even could
increase the power output significantly. Early in 1997, Hasvold
et al. found that bacteria colonize on the cathode and catalyze
the reduction of oxygen (Hasvold et al., 1997).
And in 2005, Bergel reported the presence of the biofilm on
the MFCs’ cathode surface led to efficient electron density
(Bergel et al., 2005). These findings encouraged the develop-
ment of bio-cathode MFC that the bacteria are used as bio-
catalysts to accept electrons from the cathode electrode. Up
to now, bio-cathode MFCs have attracted much attention
and have been considered as the promising MFCs (He and
the biological MFCs according to their final electron acceptors
and analyzing the advantages and disadvantages compared
with abiotic MFCs. We anticipate that bio-cathode MFCs
would have a wide application in energy recovery and micro-
bial sensor.
2. Classifications of bio-cathodes
With the development of biological cathode, many substances
including oxygen, transition metal compounds, inorganic salts
and carbon dioxide, are used as the final electron acceptor in
bio-cathode. Although the mechanism of biological electron
transfer is not completely clear, many researchers proved that
microorganisms play an important role in the bio-cathode elec-
tron-transfer process.
2.1. Oxygen as the terminal electron acceptor
Because of its high redox potential (+1.229 V) and low-cost to
supply, oxygen is the most popular terminal electron acceptor.
Microorganisms directly transfer the electrons from the anode
to oxygen or they assist the oxidation of transition metal com-
pounds for electron delivery to oxygen.
2.1.1. Oxygen as a direct electron acceptor
Marine sediment MFC is one of the earlier applications of
MFCs, which are mainly used for supplying analysis and
monitoring equipment. Early in 1997, Hasvold et al. found
in the study of seawater battery that marine life affects the cell
performance (Hasvold et al., 1997). Bacteria colonize on the
cathode surface forming slimes, which catalyze the reduction
of oxygen. This increases in catalytic activity of the cathode
and results in an increase in the on-load cell voltage from
typically 1.2 to 1.6 V. In MFCs system, different types of
sludge and sediment were mixed to obtain a cathodic inoculum
with sufficient microbial diversity. A MFC converts energy,
available in a bio-convertible substrate, directly into electricity.
This can be achieved when bacteria switch from the natural
electron acceptor, such as oxygen or nitrate, to an insoluble
acceptor, such as MFC anode (Fig. 1). These steps will remove

Please cite this article in press as: Song, H.-L. et al., Electron transfer mechanisms, characteristics and applications of biological cathode microbial fuel cells – A mini
review. Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.01.008
Electron transfer mechanisms, characteristics and applications of microbial fuel cells
2O2 + 8H + 8e
+
4H2O
Cathodic reaction
4H2O
Cathodic
2O2
Water Sediment
Figure 1
organic pollutants and recover energy at the same time.
(Clauwaert et al., 2007; Rabaey and Versterarte, 2005).
There are also some efforts to produce oxygen directly in
the cathode by applying marine algae. A MFC assembled with
an algae cathode and a R. rubrum suspension anode (sand-
blasted platinum electrodes) gave, after continuous illumina-
tion for 21 h, an open-circuit voltage of 0.96 V and a short-
circuit density of 75 lA/cm2. A cell free of organisms, operated
for comparison, gave a decrease in open-circuit potential over
7 h from 0.19 to 0.03 V. Short-circuit current density decreased
from 7.0 to 6.1 lA/cm2. And another control cell which
employed organisms and was maintained in the dark gave neg-
ligible results, similar to those of the nonbiological control.
These data demonstrated the ability of specific microorganisms
to convert light energy to electrical energy. The electrical pow-
er derived from these cells is estimated to be approximately
0.1–0.2% of that available from the incident radiation. This
low efficiency is attributed to both biological and electro-
chemical inefficiency (Berk and Canfield, 1964).
During recent years, researchers have done a lot of work to
prove that biofilm plays an important role in oxygen reduc-
tion. In 2005, Bergel conducted the research in a laboratory-s-
cale fuel cell, which was designed with a stainless steel cathode,
a platinum anode, and two separated liquid loops (Bergel
et al., 2005). The catholic loop was air-saturated, while the
anodic loop was hydrogen saturated. Seawater biofilm was
previously grown on the stainless steel cathode, and then set
up into the fuel cell. The presence of the seawater biofilm on
the stainless steel surface led to efficient catalysis of oxygen
reduction. When pH of the anode compartment increased up
to 12.5, the highest power value (270 mW/m2) was obtained
in the presence of biofilm, while a maximum power less than
2.8 mW/m2 was obtained with the cleaned cathode. Moreover,
when reducing the surface area of the cathode, the maximum
power density supplied by the PEM fuel cell in the presence
of biofilm was still increased: 325 mW/m2 were supplied with
1.34 A/m2 current density, and 64 mW/m2 were supplied with
1.89 A/m2. In 2007, Clauwaert et al. (2007) combined the
anode of acetate oxidizing tubular MFC with an open-air bio-
cathode for electricity. The maximum power production was
Please cite this article in press as: Song, H.-L. et al., Electron transfer mechanisms, characteristics and applications of biological cathode microbial fuel cells – A mini
review. Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.01.008
3
C 2H4O2 + 2H2O 2CO2+ 8H ++ 8e
Anode reaction
10cm
2CO2
Anode
8H + e
Acetate
Fermentation
Organic matter
Schematic of MFCs.
83 ± 11 W/m3 MFC for batch-fed systems (20–40% Coulom-
bic yield) and 65 ± 5 W/m3 MFC for a continuous system
with an acetate loading rate of 1.5 kg COD m 3 day 1
(90 ± 3% Coulombic yield).
Biocathodes can substantially increase the viability and sus-
tainability of MFCs has been proved. In 2005, Rabaey et al.
found that the electrons flow through a resistor to a cathode,
where the electron acceptor is reduced, and the current density
up to 1.5 mA/cm2 was obtained (Rabaey and Versterarte,
2005). They also found that some of the axenic culture
obtained from the cathode shows an increase in the power out-
put of up to threefold compared to mixed cultures. Decreasing
the activation overpotentials and the internal resistance will
strongly affect the power output. Parameters influencing the
overpotentials are the electrode surface, the electrochemical
characteristics of the electrode, the electrode potential, and
the kinetics together with the mechanism of the electron trans-
fer and the current of the MFC. Freguia et al. (2008) designed
a MFC configuration in which the effluent of an acetate-fed
anode was used as a feed for an aerated, biocatalyzed cathode.
The development of a cathodic biofilm achieved a fourfold
increase of the current output compared with the non-cat-
alyzed graphite cathode, while the pH variation in the cathode
compartment was reduced due to the additional transfer of
protons via the liquid stream. The sequential anode–cathode
configuration also provided for chemical oxygen demand
(COD) polishing at the cathode by heterotrophic bacteria, with
overall acetate removal greater than 99%. The anode achieved
an organic substrate removal of up to 2.45 kg COD/m3 of
anode liquid volume per day, at coulombic efficiencies of 65–
95%. Electron balances at the cathode revealed that the main
cathodic process was oxygen reduction to water with no sig-
nificant coulombic losses. The maximal power output during
polarization was 110 W/m3 cathode liquid volume.
Chen et al. (2010) investigated microbial community
dynamics and its electron transfer process within a biocathode
in a MFC. It was found that Gammaproteobacteria were the
most abundant division among all clone types with a percent-
age of 48.86% in the cathode compartment. They further con-
firmed that nitrate and oxygen reduction in the cathode
4 H.-L. Song et al.
compartment could be significantly enhanced by the presence
of microbes, which are able to excrete metabolites to assist
the electron transfer process either in the anode or in the cath-
ode compartment. Further research is required to identify the-
se microbial excreted metabolites.
2.1.2. Oxygen as an indirect electron acceptor
To achieve high electron transfer efficiency, manganese and iron
are used as oxygen transfer mediators under aerobic conditions.
The manganese oxides and iron salts are first reduced by the
cathode (abiotically) and then reoxidized by bacteria. During
the process, oxygen just works as an indirect electron acceptor.
Manganese is a common transition metal that is abundant
in the environment and valence state transformation (Mn (IV),
Mn (II)) can easily occur with the biocatalysis. Rhoads et al.
employed the cycle of Mn (IV) reduction and subsequent
reoxidation of Mn (II) in the cathode of a MFC and observed
a consistent production of electricity (Rhoads et al., 2005). The
whole cycle began with the reduction of MnO2 to an interme-
diate product, MnOOH, by accepting one electron from the
cathode electrode. It was followed by a further reduction of
MnOOH to Mn (II) through the acceptance of another elec-
tron, which results in the release of manganese ions. Then
the release of the divalent manganese occurs in close proximity
to the MOB-colonized electrode surface, the divalent man-
ganese was immediately reoxidized to manganese dioxide by
the MOB, and the cycle continued (Fig. 2). They demonstrated
that biomineralized manganese oxides are superior to oxygen
when used as cathodic reactants in MFCs. The current density
delivered by using biomineralized manganese oxides as the
cathodic reactant was almost 2 orders of magnitude higher
than that delivered by using oxygen. Apart from this,
Shantaram et al. (2005) applied MFCs for wireless sensor pow-
er supply, using Mn (II) involved in the response of the air-bio-
logical cathode, and got the voltage up to 211 V. Some of the
graphite felts were electrochemically pretreated to contain
manganese oxide. Electrochemical precipitation of manganese
oxides on the cathodic graphite felt decreased the start-up peri-
od with approximately 30% versus a non-treated graphite felt
(Clauwaert et al., 2007).
Similar to manganese compounds, iron reduction suggests
that organisms with such metabolic abilities play important
roles in coupling the oxidation of organic carbon to metal
Figure 2 Biological manganese deposition and reoxidation in a
biocathode reaction process.
Please cite this article in press as: Song, H.-L. et al., Electron transfer mechanisms, characteristics and applications of biological cathode microbial fuel cells – A mini
review. Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.01.008
reduction under anaerobic conditions (Nealson and Saffarini,
1994). The cycle of Fe (III) reduction and subsequent reoxida-
tion of Fe (II) can also be used in the cathode of a MFC. How-
ever, many researchers demonstrated that Iron compounds
have been used as electron mediators in abiotic cathodes. In
fact, previous studies have revealed that Fe (II) is oxidized to
Fe (III) through microbial activity by Thiobacillus fer-
rooxidans (Fig. 3). Further studies are required to examine
whether Fe (II) compounds can be oxidized by Thiobacillus
ferrooxidans with the electrons originating from an anodic
bioreaction rather than an external power supply.
Compared to using oxygen as the direct cathode, bio-cath-
ode MFCs with oxygen as the indirect cathode are more favor-
able for two reasons. First, the diffusion of oxygen from
cathode to the anode and the anode potential can both be
reduced so that electromotive force of MFCs increased.
Second, it can also improve the mass transfer efficiency of
electron acceptor, which was controlled by the mass transfer
resistance.
2.2. Inorganic salts as the electron acceptor
Under anaerobic conditions, nitrate and sulfate directly accept
electrons from a cathode electrode through microbial metabo-
lism. With a low content of oxygen, the oxygen is inhibited
from spreading to the anode, and oxygen consumption (elec-
tron transport) is reduced that may lead to the loss of coulomb
efficiency.
MFCs with NO3 as electron acceptors in the electrode reac-
tion were initially applied to the electrode-biofilm reactor
(BER). The basic principle is with imposing a certain current,
the microbes utilizing electron transferred or hydrogen pro-
duced from cathode to finish the reduction of nitrate to nitro-
gen gas. This reaction helps realizing denitrification under low-
carbon or no carbon source and avoiding adding more carbon
source in the treatment process. Holmes et al. found that both
groups of enriched organisms are involved in nitrogen trans-
formations such as ammonia oxidation and denitrification,
and proved the presence of nitrogen cycling at the cathode
(Holmes et al., 2004). Gregory et al. showed that electrodes
may serve as a direct electron donor for nitrate reduction to
nitrite (Gregory et al., 2004). Park et al. detected nitrate diffuse
from the bulk solution into the cathode biofilm and then be
Figure 3 Biological iron deposition and reoxidation in a
biocathode reaction process.
Electron transfer mechanisms, characteristics and applications of microbial fuel cells
biologically reduced to nitrogen gas by the hydrogen produced
with the electrolysis of water in the biofilm (Park et al., 2005).
Virdis et al. designed and demonstrated a novel process con-
figuration that achieves both carbon and nitrogen removal
using MFC (Virdis et al., 2008). Although redox potential of
sulfate is very low and its ability to receive electronic receptor
is much weaker than the nitrate, the researchers are still opti-
mistic about the potential that sulfate can be used as the cath-
ode electron acceptor because its reduction does not require
strict anaerobic conditions. Cord-Ruwisch and Widdel found
that metallic iron without application of an external elec-
tron-motive force is in fact used as a source of reducing equiva-
lents for dissimilatory reduction of sulfate (Cord-Ruwisch and
Widdel, 1986). The reducing equivalents were obviously mole-
cular hydrogen formed by the cathodic reaction of iron with
protons from water. Goldner et al. investigated the nutrient
requirement of sulfate-reducing bacteria when they were
applied to biocathodes in a MFC with an active metal anode
(Goldner et al., 1963). Their results demonstrated that hydro-
gen oxidation was accomplished by an enriched culture of D.
desulfuricans in seawater, containing a small amount of yeast
extract and ammonium ions.
2.3. Others
Apart from the above ones we are talking about, many com-
pounds such as urea, fumarate and carbon dioxide can be used
as electron acceptor. Two MFCs were specially designed to
increase the metabolism efficiency and energy conservation
(Park et al., 1999; Park and Zeikus, 1999). The electrochemical
bioreactor (ECB) system was separated into anode and cath-
ode compartments by a cation-selective membrane septum (di-
ameter [u] = 22 mm for type I and [u] = 64 mm for type II);
3.5 X cm 2 in 0.25 N NaOH). The anode and cathode were set
up by woven graphite felt (6 mm thick; 0.47 m2 g 1 available
surface area). A platinum wire (u = 0.5 mm; <1.0 X cm 2)
was attached to the graphite felt with graphite epoxy
(<1.0 X cm 2). The electrical resistance between anode and
cathode was < 1.0 kX. The weight of both electrodes was
adjusted to 0.4 g (surface area, 0.188 m2) for system I and
3.0 g (surface area, 1.41 m2) for system II. Park et al. found
that in the MFC with cathode of constant potential balance,
microbes (respectively, methanogen and Actinobacillus suc-
cinogenes) reduced carbon dioxide to methane and fumarate
to succinate. However, the redox potential of CO2/CH4 and
fumaric acid salt/succinic acid salt (respectively, 0.24 V and
+0.03 V) was very small, and this stimulated them to do fur-
ther research. They investigated the growth of Actinobacillus
on glucose plus electrically reduced neutral red (NR) in an
ECB system versus on glucose alone, and found that electrical-
ly reduced NR enhances glucose consumption, growth, and
succinate production by about 20% while it decreases acetate
production by about 50%. The rate of fumarate reduction to
succinate by purified membranes was twofold higher with elec-
trically reduced NR than with hydrogen as the electron donor.
Thus, NR appears to enable Actinobacillus succinogenes to
utilize electricity as a significant source of metabolic reducing
power.
Despite the voltage output was quite small and it could not
be applied into practical system, Park et al. pointed out that
Anaerobiospirillum and Actinobacillus species produce high
levels of succinate (35 and 95 g/l, respectively) during glucose
Please cite this article in press as: Song, H.-L. et al., Electron transfer mechanisms, characteristics and applications of biological cathode microbial fuel cells – A mini
review. Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.01.008
5
fermentation because hydrogen serves as an additional elec-
tron donor for metabolism. This could be exploited as an
important application of this kind of biocathode MFC because
succinic acid has many industrial uses (Samuelov et al., 1990).
3. Advantages and disadvantages
Achievements with bio-cathode MFCs over the past 3–4 years
have been particularly impressive. The versatility of bio-cath-
ode enables us to use not only metal ions but also con-
taminants as possible electron acceptors. However, there still
exist some problems which may discourage the practical appli-
cation. This section reviews the advantages and disadvantages
of bio-cathode MFCs compared with abiotic MFCs.
3.1. Advantages of bio-cathode
3.1.1. Lower expense
The cost of construction and operation of bio-cathode MFCs
are lower than abiotic MFCs. The most common types of cat-
alysts of non-biological cathode are Pt including Pt-coated
metals, transition metal elements and ferricyanide. Pt is such
a kind of efficient metal that the catalytic reaction with the
Pt-catalyzed electrodes can improve the electrical properties
of a MFC nearly 4-fold. However, Pt is expensive, greatly
increases the cost of constructing a MFC, and is not suitable
for large-scale application. Transition metals such as iron
and cobalt are also available electron mediators because they
can switch among their redox states rapidly. Cheng et al. indi-
cated that the cathode potential was reduced slightly (20–
40 mV) when Pt loadings were decreased from 2 to 0.1 mg/
cm2 (Cheng and Logan, 2006). They also found that when
the Pt loading on cathode was reduced to 0.1 mg/cm2, the max-
imum power density of MFC was reduced on average by 19%
(379 ± 5 to 301 ± 15 mW/m2; Nafion binder). Power densities
with CoTMPP were only 12% (369 ± 8 mW/m2) lower over
25 cycles than those obtained with Pt (0.5 mg/cm2; Nafion bin-
der). Precious metal Pt is a kind of ideal abiotic cathode cata-
lyst. However, its wide application is restricted by the high
cost. Another cobalt material CoTMPP faces the same prob-
lem. The abiotic cathode catalysts need to be replaced con-
tinually and would increase maintenance costs. Due to the
same reason that compared with microorganisms, exorbitant
price of metal has been a crucial factor constraining MFC’s
commercial application. Fortunately, biological cathode
MFC does not need metal catalysts or artificial electron med-
iators because microorganisms can function as catalysts to
assist the electron transfer.
3.1.2. Improved sustainability
Bio-cathodes can improve MFCs sustainability because prob-
lems with sulfur poisoning of platinum or consumption replen-
ishment of electron mediator will be eliminated (Bergel et al.,
2005). Take Pt for instance, Pt loading in both catalysts below
0.1 mg/cm2 is more prone to lead to catalyst poisoning
(Trapananti, 2008); therefore, its application has been limited.
Moreover, the oxide layer (PtO) after a long-time running
would reduce the electrode activity. When it comes to the fer-
ricyanide, troubles still exist. People utilize the circle that when
[Fe (CN)6]3 is reduced to [Fe (CN)6]4 as soon as it receives
electrons, it will be oxidized to [Fe (CN)6]3 by oxygen.
6 H.-L. Song et al.
However, this circle is not ideally substance conservation
because [Fe (CN)6]4 cannot totally be oxidized (Jang et al.,
2004). In other words, electrolyte needs to be replaced regular-
ly. These obstacles can be overcome easily by bio-cathodes,
which is environmental friendly and sustainably. In the system
of bio-cathode MFCs, the heavy metal catalysts are replaced
by microbes with high catalytic efficiency. With the aging of
biofilm, the microbes’ metabolic rates get lower and new mem-
branes grow automatically, which can take place of the old
ones. And there is no need to add extra electrolytes regularly
due to this way.
3.1.3. Easy improvement
Many factors including cathode material, electrode surface,
electrode spacing, configuration, buffer solution properties
and concentration of substrate have been proved to be associ-
ated with the performance of MFCs’ power output. For
instance, increasing cathode surface area and retaining a
relatively small area of the anode have been recommended
widely to achieve the cathodic reaction rate in abiotic cathode
MFCs (Fan et al., 2007; Logan, 2009). When it comes to bio-
cathode MFCs, people can adopt more methods and easier
actions to increase the production efficiency. In bio-cathode
MFCs, increasing cathode surface area would apparently
make room for more quantity of catalyst bacteria to live on,
which would result in the decline of electrode over potential,
improving cathode potential and power output (Kawai et al.,
2000). Moreover, the characteristics of surface functional
group and surface roughness have a significant influence on
the initial adhesion and subsequent colonization processes
(Tang et al., 2007).
3.2. Disadvantages of bio-cathode
3.2.1. Fluctuation of pH
Due to proton transport through the Nafion seemed to be
slower than the proton production rate in the anode chamber
and the proton consumption rate in the cathode chamber, a
decreasing pH in the anode chamber and an increasing pH
in the cathode chamber were happened during the operation
of two-chamber MFC (Gil et al., 2003; Rozendal et al.,
2007). Improvements in the system will soon result in power
generation that is dependent on the capabilities of the microor-
ganisms. As microorganisms’ metabolism activity is directly
affected by the pH of the environment, the continuing shift
would result in the fluctuation of both voltage output and
cathode potential. This troublesome might be solved if using
non-membrane bio-cathode MFC and oxygen might diffuse
directly into the anode (Liu and Logan, 2004). In their experi-
ment, the MFC consisted of an anode and cathode placed on
opposite side in a plastic (Plexiglas) cylindrical chamber 4 cm
long by 3 cm in diameter. The anode electrode was made of
Toray carbon paper (without wet proofing; E-Tek) and did
not contain a catalyst. The carbon electrode/PEM cathode
(CE-PEM) was manufactured by bonding the PEM directly
onto a flexible carbon-cloth electrode containing 0.5 mg/cm2
of Pt catalyst (E-Tek). The cathode used in the absence of
the PEM was a more rigid carbon paper containing 0.35 mg/
cm2 of Pt (E-Tek). Platinum wire was used to connect the cir-
cuit and results in the potential for a maximum oxygen flux of
0.05 mg/h (CE-PEM). In the absence of the PEM, the oxygen
Please cite this article in press as: Song, H.-L. et al., Electron transfer mechanisms, characteristics and applications of biological cathode microbial fuel cells – A mini
review. Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.01.008
flux could reach 0.187 mg/h (CE). In the presence of the PEM,
values obtained for oxygen diffusivities through the PEM are
consistent with oxygen diffusion results for hydrogen fuel cells.
In the absence of the PEM, however, the rate of oxygen trans-
fer into the anode chamber substantially increased. Some
attempts have also been made to enhance current generation
from the fuel cell by lowering the oxygen diffusion, including
the uses of ferricyanide as a cathode mediator and of a plat-
inum-coated graphite electrode (Jang et al., 2004).
3.2.2. Material of cathode
The material of cathode is another problem. Carbon paper,
cloth, graphite, woven graphite, graphite granules and brushes
have been used to act as MFC’S cathode (Logan, 2008). Com-
pared with no bio-cathode MFC, ideal bio-cathode materials
are bound to have large surface area as well as tough appear-
ance which offer higher possibility for microbes to live on, and
which would result in the decline of electrode over potential,
improving cathode potential and power output (Logan,
2009). This was also confirmed by You et al.; however, the
most suitable material has not yet been determined (You
et al., 2009). They provide a demonstration of graphite fiber
brush (GFB) used as bio-cathode material in MFC for more
efficient and sustainable electricity recovery from organic
substances.
3.2.3. Others
In a short few years, power increased to 96 W/m3 using a phos-
phate buffer, and further to 115 W/m3 using an ammonia-
treated electrode. The combined effects of these two treatments
boosted power production by 48% compared to previous
results using this air–cathode MFC (Cheng and Logan,
2006). However, compared with conventional water treatment
technologies, recommended value of 400 W/m3 is not even
enough. If bio-cathode MFCs are aimed at large commercial
application, the power output ought to be enhanced. Com-
pared with abiotic cathode MFCs, bio-cathode ones are more
limited by the activity of microorganisms. Efforts could be
made to increase temperature or balance pH to stimulate the
highest rate of metabolism of bacteria. Furthermore, new cul-
ture of microorganisms with high metabolism and strong sur-
vivability might be introduced.
4. Applications
Bio-cathodes are a welcome advancement in the quest to
implement MFCs for practical applications, such as waste-
water treatment and sediment MFCs because of potential cost
savings, waste removal, and operational sustainability. Large
amount of researches about abiotic MFCs of being used in
wastewater treatment to remove organics, electricity and
hydrogen generation have been performed. The investigations
up to now suggest that the applications of bio-cathode MFCs
mainly relate to simultaneous electricity generation and
nitrification.
Conventional wastewater treatments are aimed at removing
the impurities with external forces but ignoring the environ-
mental self-recovery. Therefore, the treatment process is not
a sustainable or economic one. Fortunately, this disadvantage
could be overcome if bio-cathode MFCs were applied.
Inoculating nitrifying bacteria in the cathode chamber could
Electron transfer mechanisms, characteristics and applications of microbial fuel cells
achieve simultaneous nitrification and electricity production.
Nitrification process and the power production process in
the same area not only take full advantage of dissolved oxygen,
saving aeration energy consumption, but also the nitrification
produces extra proton, effectively avoiding the cathode’s pH
fluctuation caused by the electric production process. Xie
et al. confirmed that the maximum nominal current and max-
imum power density were 47 mA and 45.50 W/m3, respectively
(Xie et al., 2010). They also constructed a coupled MFCs sys-
tem for simultaneous removal of carbon and nitrogen from a
synthetic wastewater by using oxic/anoxic – bio-cathode
MFCs (Xie et al., 2011). The system composed of an O-
MFC and an A-MFC. Each MFC was made up of a middle
anode and a two-sideward cathode, and the two-sideward
cathode was placed at the two sides of the anode chamber.
Synthetic wastewater was fed into the O-MFC and A-MFC
anode chambers using two peristaltic pumps, respectively.
The effluents from the two anode chambers were subsequently
directed into the two cathode side chambers of the O-MFC for
aerobic nitrification. Oxygenation of the cathodic vessel was
supplied by an air pump, and the airflow was adjusted with
an airflow rotameter. The effluent from the O-MFC cathode
chambers was fed into the A-MFC cathode chambers for
electrochemical denitrification. Part of the effluent from the
A-MFC cathode chamber was recirculated into the O-MFC
cathode chamber for deep nitrification. A maximum nominal
current of 52.1 ± 0.9 mA was obtained by the A-MFC when
a 5 X. was applied on the reactor, while 22.7 ± 0.1 mA was
instead obtained at 20 X. The specific currents were
26.1 ± 0.5 A/m3 net cathodic compartment (NCC) and
11.4 ± 0.0 A/ m3 NCC, respectively. The A-MFC produced
a maximum power production of 6.8 ± 0.2 W/m3 NCC at
the resistance of 5X. The specific current and specific power
density of the O-MFC were 19.4 ± 0.1 A/m3 NCC and
15.1 ± 0.0 W/m3 NCC, respectively. In addition, the coupled
MFC system achieved a maximum COD, NH+ 4 –N and TN
removal of 98.8%, 97.4% and 97.3%, respectively. Moreover,
operation parameters, especially external resistance and influ-
ent flow ratio, which have great effects on nitrogen removal,
can be accommodated according to the COD/N ratio of
wastewater.
5. Prospect
Bio-cathode MFCs have the advantages of low cost, uninter-
rupted operation and reduction of secondary pollution, etc.
However, few studies have described bio-cathodes completely
and comprehensively. And the efforts are always being made
to improve the performance of bio-cathodes. First of all, it
would be important in the future to look for cheap and effi-
cient electrode materials. Researching and developing elec-
trodes appropriate for bacteria living and comparatively of
low resistance would be favorable for large-scale application
of bio-cathode MFCs. Secondly, the dominant bacteria with
sustainable electrochemically active should be cultured and
acclimated for wastewater treatment. Thirdly, it should be
admitted that the power output of bio-cathode MFC is impos-
sible to weigh against conventional chemical fuel cells, which
means there is a huge potential that bio-cathodes could be
improved. We are confident that the application of bio-
cathodes in MFCs will prosper in the fields of practical
Please cite this article in press as: Song, H.-L. et al., Electron transfer mechanisms, characteristics and applications of biological cathode microbial fuel cells – A mini
review. Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.01.008
7
wastewater treatment to enhance the sustainable and profitable
as well as sediment MFCs to power small electronic sensors in
the abysmal sea where electrical energy is hard to supply.
Acknowledgments
The authors would like to acknowledge the financial support
from the Provincial Natural Science Foundation of Jiangsu,
China (BK20141117) and the National Science Foundation
of China (Grant No. 51109038).
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