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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


the biological MFCs according to their final electron acceptors
After being stricken by energy crises, people have realized the and analyzing the advantages and disadvantages compared
urgency to change the energy structure, which depends too with abiotic MFCs. We anticipate that bio-cathode MFCs
strongly on fossil fuels. Some renewable and sustainable would have a wide application in energy recovery and micro-
resources are proposed to alleviate the situation, among which bial sensor.
bioenergy is considered as the most efficient way. Inspired by
Luigi Galvani (1737–1798), an Italian physician and also a 2. Classifications of bio-cathodes
physicist, found that frogs tissues are endowed with an intrin-
sic electricity, which proved the existence of animal electricity With the development of biological cathode, many substances
(Piccolino, 1998). Michael C. Potter established the first micro- including oxygen, transition metal compounds, inorganic salts
bial fuel cell (MFC) in 1911, and he demonstrated a current and carbon dioxide, are used as the final electron acceptor in
flow between two electrodes emerged in a bacterial culture bio-cathode. Although the mechanism of biological electron
and in sterile medium (He and Aneenent, 2006). The current transfer is not completely clear, many researchers proved that
design concept of MFC came into existence in 1977 with the microorganisms play an important role in the bio-cathode elec-
work by Karube et al. (1977). However, little was known about tron-transfer process.
how MFCs fecundated at that time. In 1999, Kim et al. suc-
cessfully found electricity generation uses MFCs, which were 2.1. Oxygen as the terminal electron acceptor
regarded as a milestone of the development of MFCs (Kim
et al., 1999).
Consisting of an anode chamber and a cathode chamber, Because of its high redox potential (+1.229 V) and low-cost to
which are separated by the proton exchange membranes, a supply, oxygen is the most popular terminal electron acceptor.
MFC’s power can be generated from the oxidation of organic Microorganisms directly transfer the electrons from the anode
matter by bacteria at the anode, with reduction of oxygen at to oxygen or they assist the oxidation of transition metal com-
the cathode (Logan et al., 2005). According to numerous find- pounds for electron delivery to oxygen.
ings, the configurations of MFCs are quite various, including
air–cathode MFCs, aqueous cathodes using dissolved oxygen, 2.1.1. Oxygen as a direct electron acceptor
and two-chamber reactors with soluble catholytes or poised Marine sediment MFC is one of the earlier applications of
potentials, tubular packed bed reactors and so on. In these dif- MFCs, which are mainly used for supplying analysis and
ferent configurations of MFCs, microbes only exist in the monitoring equipment. Early in 1997, Hasvold et al. found
anode chamber. However, some investigations found that bac- in the study of seawater battery that marine life affects the cell
teria grew quite inevitably in the cathodes and even could performance (Hasvold et al., 1997). Bacteria colonize on the
increase the power output significantly. Early in 1997, Hasvold cathode surface forming slimes, which catalyze the reduction
et al. found that bacteria colonize on the cathode and catalyze of oxygen. This increases in catalytic activity of the cathode
the reduction of oxygen (Hasvold et al., 1997). and results in an increase in the on-load cell voltage from
And in 2005, Bergel reported the presence of the biofilm on typically 1.2 to 1.6 V. In MFCs system, different types of
the MFCs’ cathode surface led to efficient electron density sludge and sediment were mixed to obtain a cathodic inoculum
(Bergel et al., 2005). These findings encouraged the develop- with sufficient microbial diversity. A MFC converts energy,
ment of bio-cathode MFC that the bacteria are used as bio- available in a bio-convertible substrate, directly into electricity.
catalysts to accept electrons from the cathode electrode. Up This can be achieved when bacteria switch from the natural
to now, bio-cathode MFCs have attracted much attention electron acceptor, such as oxygen or nitrate, to an insoluble
and have been considered as the promising MFCs (He and 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 3

C 2H4O2 + 2H2O 2CO2+ 8H ++ 8e


2O2 + 8H + 8e
+
4H2O
Anode reaction
Cathodic reaction

10cm
2CO2
4H2O

Cathodic Anode
8H + e
Acetate
2O2
Fermentation

Organic matter
Water Sediment

Figure 1 Schematic of MFCs.

organic pollutants and recover energy at the same time. 83 ± 11 W/m3 MFC for batch-fed systems (20–40% Coulom-
(Clauwaert et al., 2007; Rabaey and Versterarte, 2005). bic yield) and 65 ± 5 W/m3 MFC for a continuous system
There are also some efforts to produce oxygen directly in with an acetate loading rate of 1.5 kg COD m 3 day 1
the cathode by applying marine algae. A MFC assembled with (90 ± 3% Coulombic yield).
an algae cathode and a R. rubrum suspension anode (sand- Biocathodes can substantially increase the viability and sus-
blasted platinum electrodes) gave, after continuous illumina- tainability of MFCs has been proved. In 2005, Rabaey et al.
tion for 21 h, an open-circuit voltage of 0.96 V and a short- found that the electrons flow through a resistor to a cathode,
circuit density of 75 lA/cm2. A cell free of organisms, operated where the electron acceptor is reduced, and the current density
for comparison, gave a decrease in open-circuit potential over up to 1.5 mA/cm2 was obtained (Rabaey and Versterarte,
7 h from 0.19 to 0.03 V. Short-circuit current density decreased 2005). They also found that some of the axenic culture
from 7.0 to 6.1 lA/cm2. And another control cell which obtained from the cathode shows an increase in the power out-
employed organisms and was maintained in the dark gave neg- put of up to threefold compared to mixed cultures. Decreasing
ligible results, similar to those of the nonbiological control. the activation overpotentials and the internal resistance will
These data demonstrated the ability of specific microorganisms strongly affect the power output. Parameters influencing the
to convert light energy to electrical energy. The electrical pow- overpotentials are the electrode surface, the electrochemical
er derived from these cells is estimated to be approximately characteristics of the electrode, the electrode potential, and
0.1–0.2% of that available from the incident radiation. This the kinetics together with the mechanism of the electron trans-
low efficiency is attributed to both biological and electro- fer and the current of the MFC. Freguia et al. (2008) designed
chemical inefficiency (Berk and Canfield, 1964). a MFC configuration in which the effluent of an acetate-fed
During recent years, researchers have done a lot of work to anode was used as a feed for an aerated, biocatalyzed cathode.
prove that biofilm plays an important role in oxygen reduc- The development of a cathodic biofilm achieved a fourfold
tion. In 2005, Bergel conducted the research in a laboratory-s- increase of the current output compared with the non-cat-
cale fuel cell, which was designed with a stainless steel cathode, alyzed graphite cathode, while the pH variation in the cathode
a platinum anode, and two separated liquid loops (Bergel compartment was reduced due to the additional transfer of
et al., 2005). The catholic loop was air-saturated, while the protons via the liquid stream. The sequential anode–cathode
anodic loop was hydrogen saturated. Seawater biofilm was configuration also provided for chemical oxygen demand
previously grown on the stainless steel cathode, and then set (COD) polishing at the cathode by heterotrophic bacteria, with
up into the fuel cell. The presence of the seawater biofilm on overall acetate removal greater than 99%. The anode achieved
the stainless steel surface led to efficient catalysis of oxygen an organic substrate removal of up to 2.45 kg COD/m3 of
reduction. When pH of the anode compartment increased up anode liquid volume per day, at coulombic efficiencies of 65–
to 12.5, the highest power value (270 mW/m2) was obtained 95%. Electron balances at the cathode revealed that the main
in the presence of biofilm, while a maximum power less than cathodic process was oxygen reduction to water with no sig-
2.8 mW/m2 was obtained with the cleaned cathode. Moreover, nificant coulombic losses. The maximal power output during
when reducing the surface area of the cathode, the maximum polarization was 110 W/m3 cathode liquid volume.
power density supplied by the PEM fuel cell in the presence Chen et al. (2010) investigated microbial community
of biofilm was still increased: 325 mW/m2 were supplied with dynamics and its electron transfer process within a biocathode
1.34 A/m2 current density, and 64 mW/m2 were supplied with in a MFC. It was found that Gammaproteobacteria were the
1.89 A/m2. In 2007, Clauwaert et al. (2007) combined the most abundant division among all clone types with a percent-
anode of acetate oxidizing tubular MFC with an open-air bio- age of 48.86% in the cathode compartment. They further con-
cathode for electricity. The maximum power production was firmed that nitrate and oxygen reduction in the cathode

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
4 H.-L. Song et al.

compartment could be significantly enhanced by the presence reduction under anaerobic conditions (Nealson and Saffarini,
of microbes, which are able to excrete metabolites to assist 1994). The cycle of Fe (III) reduction and subsequent reoxida-
the electron transfer process either in the anode or in the cath- tion of Fe (II) can also be used in the cathode of a MFC. How-
ode compartment. Further research is required to identify the- ever, many researchers demonstrated that Iron compounds
se microbial excreted metabolites. have been used as electron mediators in abiotic cathodes. In
fact, previous studies have revealed that Fe (II) is oxidized to
2.1.2. Oxygen as an indirect electron acceptor Fe (III) through microbial activity by Thiobacillus fer-
To achieve high electron transfer efficiency, manganese and iron rooxidans (Fig. 3). Further studies are required to examine
are used as oxygen transfer mediators under aerobic conditions. whether Fe (II) compounds can be oxidized by Thiobacillus
The manganese oxides and iron salts are first reduced by the ferrooxidans with the electrons originating from an anodic
cathode (abiotically) and then reoxidized by bacteria. During bioreaction rather than an external power supply.
the process, oxygen just works as an indirect electron acceptor. Compared to using oxygen as the direct cathode, bio-cath-
Manganese is a common transition metal that is abundant ode MFCs with oxygen as the indirect cathode are more favor-
in the environment and valence state transformation (Mn (IV), able for two reasons. First, the diffusion of oxygen from
Mn (II)) can easily occur with the biocatalysis. Rhoads et al. cathode to the anode and the anode potential can both be
employed the cycle of Mn (IV) reduction and subsequent reduced so that electromotive force of MFCs increased.
reoxidation of Mn (II) in the cathode of a MFC and observed Second, it can also improve the mass transfer efficiency of
a consistent production of electricity (Rhoads et al., 2005). The electron acceptor, which was controlled by the mass transfer
whole cycle began with the reduction of MnO2 to an interme- resistance.
diate product, MnOOH, by accepting one electron from the
cathode electrode. It was followed by a further reduction of 2.2. Inorganic salts as the electron acceptor
MnOOH to Mn (II) through the acceptance of another elec-
tron, which results in the release of manganese ions. Then Under anaerobic conditions, nitrate and sulfate directly accept
the release of the divalent manganese occurs in close proximity electrons from a cathode electrode through microbial metabo-
to the MOB-colonized electrode surface, the divalent man- lism. With a low content of oxygen, the oxygen is inhibited
ganese was immediately reoxidized to manganese dioxide by from spreading to the anode, and oxygen consumption (elec-
the MOB, and the cycle continued (Fig. 2). They demonstrated tron transport) is reduced that may lead to the loss of coulomb
that biomineralized manganese oxides are superior to oxygen efficiency.
when used as cathodic reactants in MFCs. The current density MFCs with NO3 as electron acceptors in the electrode reac-
delivered by using biomineralized manganese oxides as the tion were initially applied to the electrode-biofilm reactor
cathodic reactant was almost 2 orders of magnitude higher (BER). The basic principle is with imposing a certain current,
than that delivered by using oxygen. Apart from this, the microbes utilizing electron transferred or hydrogen pro-
Shantaram et al. (2005) applied MFCs for wireless sensor pow- duced from cathode to finish the reduction of nitrate to nitro-
er supply, using Mn (II) involved in the response of the air-bio- gen gas. This reaction helps realizing denitrification under low-
logical cathode, and got the voltage up to 211 V. Some of the carbon or no carbon source and avoiding adding more carbon
graphite felts were electrochemically pretreated to contain source in the treatment process. Holmes et al. found that both
manganese oxide. Electrochemical precipitation of manganese groups of enriched organisms are involved in nitrogen trans-
oxides on the cathodic graphite felt decreased the start-up peri- formations such as ammonia oxidation and denitrification,
od with approximately 30% versus a non-treated graphite felt and proved the presence of nitrogen cycling at the cathode
(Clauwaert et al., 2007). (Holmes et al., 2004). Gregory et al. showed that electrodes
Similar to manganese compounds, iron reduction suggests may serve as a direct electron donor for nitrate reduction to
that organisms with such metabolic abilities play important nitrite (Gregory et al., 2004). Park et al. detected nitrate diffuse
roles in coupling the oxidation of organic carbon to metal from the bulk solution into the cathode biofilm and then be

Figure 2 Biological manganese deposition and reoxidation in a Figure 3 Biological iron deposition and reoxidation in a
biocathode reaction process. 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
Electron transfer mechanisms, characteristics and applications of microbial fuel cells 5

biologically reduced to nitrogen gas by the hydrogen produced fermentation because hydrogen serves as an additional elec-
with the electrolysis of water in the biofilm (Park et al., 2005). tron donor for metabolism. This could be exploited as an
Virdis et al. designed and demonstrated a novel process con- important application of this kind of biocathode MFC because
figuration that achieves both carbon and nitrogen removal succinic acid has many industrial uses (Samuelov et al., 1990).
using MFC (Virdis et al., 2008). Although redox potential of
sulfate is very low and its ability to receive electronic receptor 3. Advantages and disadvantages
is much weaker than the nitrate, the researchers are still opti-
mistic about the potential that sulfate can be used as the cath- Achievements with bio-cathode MFCs over the past 3–4 years
ode electron acceptor because its reduction does not require have been particularly impressive. The versatility of bio-cath-
strict anaerobic conditions. Cord-Ruwisch and Widdel found ode enables us to use not only metal ions but also con-
that metallic iron without application of an external elec- taminants as possible electron acceptors. However, there still
tron-motive force is in fact used as a source of reducing equiva- exist some problems which may discourage the practical appli-
lents for dissimilatory reduction of sulfate (Cord-Ruwisch and cation. This section reviews the advantages and disadvantages
Widdel, 1986). The reducing equivalents were obviously mole- of bio-cathode MFCs compared with abiotic MFCs.
cular hydrogen formed by the cathodic reaction of iron with
protons from water. Goldner et al. investigated the nutrient 3.1. Advantages of bio-cathode
requirement of sulfate-reducing bacteria when they were
applied to biocathodes in a MFC with an active metal anode
3.1.1. Lower expense
(Goldner et al., 1963). Their results demonstrated that hydro-
gen oxidation was accomplished by an enriched culture of D. The cost of construction and operation of bio-cathode MFCs
desulfuricans in seawater, containing a small amount of yeast are lower than abiotic MFCs. The most common types of cat-
extract and ammonium ions. alysts of non-biological cathode are Pt including Pt-coated
metals, transition metal elements and ferricyanide. Pt is such
2.3. Others a kind of efficient metal that the catalytic reaction with the
Pt-catalyzed electrodes can improve the electrical properties
Apart from the above ones we are talking about, many com- of a MFC nearly 4-fold. However, Pt is expensive, greatly
pounds such as urea, fumarate and carbon dioxide can be used increases the cost of constructing a MFC, and is not suitable
as electron acceptor. Two MFCs were specially designed to for large-scale application. Transition metals such as iron
increase the metabolism efficiency and energy conservation and cobalt are also available electron mediators because they
(Park et al., 1999; Park and Zeikus, 1999). The electrochemical can switch among their redox states rapidly. Cheng et al. indi-
bioreactor (ECB) system was separated into anode and cath- cated that the cathode potential was reduced slightly (20–
ode compartments by a cation-selective membrane septum (di- 40 mV) when Pt loadings were decreased from 2 to 0.1 mg/
ameter [u] = 22 mm for type I and [u] = 64 mm for type II); cm2 (Cheng and Logan, 2006). They also found that when
3.5 X cm 2 in 0.25 N NaOH). The anode and cathode were set the Pt loading on cathode was reduced to 0.1 mg/cm2, the max-
up by woven graphite felt (6 mm thick; 0.47 m2 g 1 available imum power density of MFC was reduced on average by 19%
surface area). A platinum wire (u = 0.5 mm; <1.0 X cm 2) (379 ± 5 to 301 ± 15 mW/m2; Nafion binder). Power densities
was attached to the graphite felt with graphite epoxy with CoTMPP were only 12% (369 ± 8 mW/m2) lower over
(<1.0 X cm 2). The electrical resistance between anode and 25 cycles than those obtained with Pt (0.5 mg/cm2; Nafion bin-
cathode was < 1.0 kX. The weight of both electrodes was der). Precious metal Pt is a kind of ideal abiotic cathode cata-
adjusted to 0.4 g (surface area, 0.188 m2) for system I and lyst. However, its wide application is restricted by the high
3.0 g (surface area, 1.41 m2) for system II. Park et al. found cost. Another cobalt material CoTMPP faces the same prob-
that in the MFC with cathode of constant potential balance, lem. The abiotic cathode catalysts need to be replaced con-
microbes (respectively, methanogen and Actinobacillus suc- tinually and would increase maintenance costs. Due to the
cinogenes) reduced carbon dioxide to methane and fumarate same reason that compared with microorganisms, exorbitant
to succinate. However, the redox potential of CO2/CH4 and price of metal has been a crucial factor constraining MFC’s
fumaric acid salt/succinic acid salt (respectively, 0.24 V and commercial application. Fortunately, biological cathode
+0.03 V) was very small, and this stimulated them to do fur- MFC does not need metal catalysts or artificial electron med-
ther research. They investigated the growth of Actinobacillus iators because microorganisms can function as catalysts to
on glucose plus electrically reduced neutral red (NR) in an assist the electron transfer.
ECB system versus on glucose alone, and found that electrical-
ly reduced NR enhances glucose consumption, growth, and 3.1.2. Improved sustainability
succinate production by about 20% while it decreases acetate Bio-cathodes can improve MFCs sustainability because prob-
production by about 50%. The rate of fumarate reduction to lems with sulfur poisoning of platinum or consumption replen-
succinate by purified membranes was twofold higher with elec- ishment of electron mediator will be eliminated (Bergel et al.,
trically reduced NR than with hydrogen as the electron donor. 2005). Take Pt for instance, Pt loading in both catalysts below
Thus, NR appears to enable Actinobacillus succinogenes to 0.1 mg/cm2 is more prone to lead to catalyst poisoning
utilize electricity as a significant source of metabolic reducing (Trapananti, 2008); therefore, its application has been limited.
power. Moreover, the oxide layer (PtO) after a long-time running
Despite the voltage output was quite small and it could not would reduce the electrode activity. When it comes to the fer-
be applied into practical system, Park et al. pointed out that ricyanide, troubles still exist. People utilize the circle that when
Anaerobiospirillum and Actinobacillus species produce high [Fe (CN)6]3 is reduced to [Fe (CN)6]4 as soon as it receives
levels of succinate (35 and 95 g/l, respectively) during glucose electrons, it will be oxidized to [Fe (CN)6]3 by 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
6 H.-L. Song et al.

However, this circle is not ideally substance conservation flux could reach 0.187 mg/h (CE). In the presence of the PEM,
because [Fe (CN)6]4 cannot totally be oxidized (Jang et al., values obtained for oxygen diffusivities through the PEM are
2004). In other words, electrolyte needs to be replaced regular- consistent with oxygen diffusion results for hydrogen fuel cells.
ly. These obstacles can be overcome easily by bio-cathodes, In the absence of the PEM, however, the rate of oxygen trans-
which is environmental friendly and sustainably. In the system fer into the anode chamber substantially increased. Some
of bio-cathode MFCs, the heavy metal catalysts are replaced attempts have also been made to enhance current generation
by microbes with high catalytic efficiency. With the aging of from the fuel cell by lowering the oxygen diffusion, including
biofilm, the microbes’ metabolic rates get lower and new mem- the uses of ferricyanide as a cathode mediator and of a plat-
branes grow automatically, which can take place of the old inum-coated graphite electrode (Jang et al., 2004).
ones. And there is no need to add extra electrolytes regularly
due to this way. 3.2.2. Material of cathode
The material of cathode is another problem. Carbon paper,
3.1.3. Easy improvement cloth, graphite, woven graphite, graphite granules and brushes
Many factors including cathode material, electrode surface, have been used to act as MFC’S cathode (Logan, 2008). Com-
electrode spacing, configuration, buffer solution properties pared with no bio-cathode MFC, ideal bio-cathode materials
and concentration of substrate have been proved to be associ- are bound to have large surface area as well as tough appear-
ated with the performance of MFCs’ power output. For ance which offer higher possibility for microbes to live on, and
instance, increasing cathode surface area and retaining a which would result in the decline of electrode over potential,
relatively small area of the anode have been recommended improving cathode potential and power output (Logan,
widely to achieve the cathodic reaction rate in abiotic cathode 2009). This was also confirmed by You et al.; however, the
MFCs (Fan et al., 2007; Logan, 2009). When it comes to bio- most suitable material has not yet been determined (You
cathode MFCs, people can adopt more methods and easier et al., 2009). They provide a demonstration of graphite fiber
actions to increase the production efficiency. In bio-cathode brush (GFB) used as bio-cathode material in MFC for more
MFCs, increasing cathode surface area would apparently efficient and sustainable electricity recovery from organic
make room for more quantity of catalyst bacteria to live on, substances.
which would result in the decline of electrode over potential,
improving cathode potential and power output (Kawai et al., 3.2.3. Others
2000). Moreover, the characteristics of surface functional In a short few years, power increased to 96 W/m3 using a phos-
group and surface roughness have a significant influence on phate buffer, and further to 115 W/m3 using an ammonia-
the initial adhesion and subsequent colonization processes treated electrode. The combined effects of these two treatments
(Tang et al., 2007). boosted power production by 48% compared to previous
results using this air–cathode MFC (Cheng and Logan,
3.2. Disadvantages of bio-cathode 2006). However, compared with conventional water treatment
technologies, recommended value of 400 W/m3 is not even
3.2.1. Fluctuation of pH enough. If bio-cathode MFCs are aimed at large commercial
application, the power output ought to be enhanced. Com-
Due to proton transport through the Nafion seemed to be
pared with abiotic cathode MFCs, bio-cathode ones are more
slower than the proton production rate in the anode chamber
limited by the activity of microorganisms. Efforts could be
and the proton consumption rate in the cathode chamber, a
made to increase temperature or balance pH to stimulate the
decreasing pH in the anode chamber and an increasing pH
highest rate of metabolism of bacteria. Furthermore, new cul-
in the cathode chamber were happened during the operation
ture of microorganisms with high metabolism and strong sur-
of two-chamber MFC (Gil et al., 2003; Rozendal et al.,
vivability might be introduced.
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 4. Applications
affected by the pH of the environment, the continuing shift
would result in the fluctuation of both voltage output and Bio-cathodes are a welcome advancement in the quest to
cathode potential. This troublesome might be solved if using implement MFCs for practical applications, such as waste-
non-membrane bio-cathode MFC and oxygen might diffuse water treatment and sediment MFCs because of potential cost
directly into the anode (Liu and Logan, 2004). In their experi- savings, waste removal, and operational sustainability. Large
ment, the MFC consisted of an anode and cathode placed on amount of researches about abiotic MFCs of being used in
opposite side in a plastic (Plexiglas) cylindrical chamber 4 cm wastewater treatment to remove organics, electricity and
long by 3 cm in diameter. The anode electrode was made of hydrogen generation have been performed. The investigations
Toray carbon paper (without wet proofing; E-Tek) and did up to now suggest that the applications of bio-cathode MFCs
not contain a catalyst. The carbon electrode/PEM cathode mainly relate to simultaneous electricity generation and
(CE-PEM) was manufactured by bonding the PEM directly nitrification.
onto a flexible carbon-cloth electrode containing 0.5 mg/cm2 Conventional wastewater treatments are aimed at removing
of Pt catalyst (E-Tek). The cathode used in the absence of the impurities with external forces but ignoring the environ-
the PEM was a more rigid carbon paper containing 0.35 mg/ mental self-recovery. Therefore, the treatment process is not
cm2 of Pt (E-Tek). Platinum wire was used to connect the cir- a sustainable or economic one. Fortunately, this disadvantage
cuit and results in the potential for a maximum oxygen flux of could be overcome if bio-cathode MFCs were applied.
0.05 mg/h (CE-PEM). In the absence of the PEM, the oxygen Inoculating nitrifying bacteria in the cathode chamber could

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 7

achieve simultaneous nitrification and electricity production. wastewater treatment to enhance the sustainable and profitable
Nitrification process and the power production process in as well as sediment MFCs to power small electronic sensors in
the same area not only take full advantage of dissolved oxygen, the abysmal sea where electrical energy is hard to supply.
saving aeration energy consumption, but also the nitrification
produces extra proton, effectively avoiding the cathode’s pH Acknowledgments
fluctuation caused by the electric production process. Xie
et al. confirmed that the maximum nominal current and max- The authors would like to acknowledge the financial support
imum power density were 47 mA and 45.50 W/m3, respectively from the Provincial Natural Science Foundation of Jiangsu,
(Xie et al., 2010). They also constructed a coupled MFCs sys- China (BK20141117) and the National Science Foundation
tem for simultaneous removal of carbon and nitrogen from a of China (Grant No. 51109038).
synthetic wastewater by using oxic/anoxic – bio-cathode
MFCs (Xie et al., 2011). The system composed of an O- References
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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
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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