Applied Surface Science 317 (2014) 84–89

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Graphite coated with manganese oxide/multiwall carbon nanotubes

composites as anodes in marine benthic microbial fuel cells
Yubin Fu ∗ , Jian Yu, Yelong Zhang, Yao Meng
Institute of Materials Science and Engineering, Ocean University of China, Qingdao 266100, China

a r t i c l e i n f o a b s t r a c t

Article history: Improving anode performance is of great significance to scale up benthic microbial fuel cells (BMFCs)
Received 19 June 2014 for its marine application to drive oceanography instruments. In this study, manganese oxide
Received in revised form 22 July 2014 (MnO2 )/multiwall carbon nanotubes (MWCNTs) composites are prepared to be as novel anodes in the
Accepted 8 August 2014
BMFCs via a direct redox reaction between permanganate ions (MnO4 − ) and MWCNTs. The results
Available online 19 August 2014
indicate that the MnO2 /MWCNTs anode has a better wettability, greater kinetic activity and higher
power density than that of the plain graphite (PG) anode. It is noted that the MnO2 (50% weight
Keywords:
percent)/MWCNTs anode shows the highest electrochemical performance among them and will be a
Manganese oxide
Modified anodes
promising material for improving bioelectricity production of the BMFCs. Finally, a synergistic mecha-
Kinetic activity nism of electron transfer shuttle of Mn ions and their redox reactions in the interface between modified
Electron transfer mechanism anode and bacteria biofilm are proposed to explain its excellent electrochemical performance.
© 2014 Published by Elsevier B.V.

1. Introduction nanotubes (CNTs) are an excellent conducting additive or support

Since microbial fuel cells (MFCs) are well-known as bioelec-
trochemical devices that harvest electrical energy from organic or
inorganic matter via the catalyzation of some bacteria, which makes
it obtain considerable attention from microbiological, environmen-
tal, and material researchers [1–3]. Reimers et al. [4] developed the
novel concept of using marine benthic MFCs (BMFCs) as a remote
source of power to drive instruments work for a long term. In gen-
eral, the BMFCs consists of an anode which is buried under marine
sediment (an anoxic zone), and connect by an electrical circuit to
the cathode which is immersed in seawater (an oxic zone) [5–7].
Recently, many researchers have studied different methods and
various types of materials for enhancing MFCs anode performance.
Whereby (i) electroactive species such as anthraquinone-1,6-
disulfonic acid (AQDS) [8], or (ii) highly conductive species such
as conducting polymers [9] and metal particles [10] have achieved
excellent performance. However, most of these methods are costly,
time impractical and usually produce large amounts of contami-
nants that can add other environmental problems. Owing to the
electro-catalytic ability of MnO2 toward the oxygen reduction
reaction (ORR), it is considered to be one of the most promis-
ing materials for the fabrication of MFCs cathode [11,12]. Carbon
template of MnO2 for offering the advantage of low resistance,
which is important for the fabrication of efficient electrode. To date,
only few studies of applying MnO2 /CNTs composites in MFCs have
been reported. Zhang et al. [13] used the MnO2 /CNTs cathode in
MFC, and achieved a maximum power density of 210 mW m−2 . Sim-
ilar results are reported by Chen et al. [14] also using MnO2 /CNTs
cathode but coated on stainless steel mesh. To the best of my
knowledge, few researches have been done on the performance
of MnO2 /CNTs as anode material.
In this study, MnO2 /MWCNTs nanocomposites with different
MnO2 contents (25%, 50% and 75 wt %) were characterized and uti-
lized as the BMFCs anode materials respectively. The performance
of the as-prepared anodes was evaluated through comparison with
that of the PG and MWCNTs. Scanning electron microscopy (SEM),
contact angle measurement and Tafel plots were applied to char-
acterize their structural and electrical properties. Furthermore, a
possible mechanism was presented for the explanation of this
work.
2. Materials and methods
2.1. MnO2 /MWCNTs nanocomposites preparation

The MWCNTs (30–50 nm in diameter, Shenzhen Nanotech

∗ Corresponding author. Tel.: +86 15953273073. Port Co., Ltd.) supported MnO2 nanocomposites were prepared
E-mail addresses: ffyybb@ouc.edu.cn, ffyybb725@vip.sina.com (Y. Fu). by the redox method as previously described [14–16]. The

http://dx.doi.org/10.1016/j.apsusc.2014.08.044
0169-4332/© 2014 Published by Elsevier B.V.
 Y. Fu et al. / Applied Surface Science 317 (2014) 84–89
MnO2 /MWCNTs composites with different percentage of MnO2
were obtained by changing the concentrations of KMnO4 . Firstly, 1 g
of MWCNTs were added into the 400 mL KMnO4 solution with dif-
ferent concentrations (0.009, 0.0287 and 0.086 M), and then stirred
continuously at 70 ◦ C for 6 h. During the synthesis, the pH of the
solution was controlled at 1 by using 1 M HCl solution. The resulting
colorless suspension was then filtered, washed several times using
distilled water, and vacuum-dried at 100 ◦ C overnight for further
analysis. Assuming that MnO4 − was completely reduced to MnO2
in all cases, the desired MnO2 /MWCNTs with loading levels of 25,
50 and 75 wt.% should be correspond to the initial KMnO4 solution
of 0.009, 0.0287 and 0.086 M, respectively.
2.2. Electrode preparation
Four types (MWCNTs, MnO2 (25%)/MWCNTs, MnO2
(50%)/MWCNTs and MnO2 (75%)/MWCNTs) of anodes (4 cm × 4 cm)
were prepared by the following procedures. Firstly, 0.2 g of as-
prepared powders was mixed with 5 mL Nafion solution to prepare
pastes, then pasting on the surface of plain graphite (PG) to
produce uniform films, finally pressing to fabricate electrodes. The
control was the PG anode.
2.3. BMFCs construction
Five separate cells were constructed by using MWCNTs, MnO2
(25%)/MWCNTs, MnO2 (50%)/MWCNTs, MnO2 (75%)/MWCNTs and
PG anode respectively, each fitted with the same graphite cathode
(4 cm × 4 cm, 2 cm thickness). In this setup, the cell was of cylin-
drical shape and made of plexiglass (7 cm in diameter, 20 cm in
height). The natural seawater and marine sediment utilized here
were fetched from the Jiaozhou Bay, Qingdao, China (36◦ 10.3 N,
120◦ 18.1 E). The anode was buried 5 cm below the sediment sur-
face, with the cathode 10 cm above the anode. Each cell experiment
was conducted in three parallels to obtain average values.
2.4. Analysis and calculation
The nanocomposite samples were structurally characterized by
X-ray diffraction (XRD), using a Macscience-M18XHF Advance X-
ray diffractometer. The morphologies of samples were compared
with a scanning electron microscope (SEM, Hitachi S-4800). The
water contact angle was measured by a contact angle meter (KRUSS
DSA100).
Tafel plots were performed with an Electrochemical Worksta-
tion (Model LK2005A, TianJin Lanlike Co., Ltd.) at scan rate of
1 mV s−1 from  = 0–100 mV, where  = 0 is the open circuit poten-
tial (OCP) of the anode versus the reference electrode. Tafel plots
were conducted in a conventional three electrode configuration:
a saturated calomel electrode (SCE) served as the reference, the
anode as the working and the cathode as the counter electrode [8].
When obtaining a steady voltage, the polarization curves and the
power density curves were monitored by varying external resis-
tances (40–7000 ). Anode potentials (vs. SCE) were measured
using a digital multimeter (Shenzhen Huayi Instrument Co., Ltd.).
Power (mW) was calculated by using the equation: P = IV, where
I and V represent current (A) and voltage (V) respectively. Power
density (mW m−2 ) and current density (mA m−2 ) were calculated
by the anode projected surface area (1.6 × 10−3 m2 ) [17].
3. Results and discussion
3.1. Structure characterization
XRD was first employed to confirm the successful fabrication of
the MnO2 /MWCNTs composite. Fig. 1 shows the XRD patterns of
85
Fig. 1. X-ray diffraction patterns of (a) MWCNTs and MnO2 /MWCNTs nanocompos-
ites with different MnO2 contents: (b) 25%, (c) 50% and (d) 75%.
the pristine MWCNTs and the MnO2 /MWCNTs composites. In the
pattern of the pristine MWCNTs sample, two well-defined peaks
are observed at around 2 = 26◦ and 44◦ associated with the (0 0 2)
and (1 0 0) diffractions of the graphite (Fig. 1 (a)) [14]. From Fig. 1d,
characteristic peak at 2 = 44◦ is also observed in both patterns
of the MnO2 /MWCNTs composites, indicating the MWCNTs com-
bined into MnO2 have XRD signal nearly identical to the pristine.
The intense diffraction peaks at 2 = 12◦ , 37◦ and 66◦ in the pat-
tern of the MnO2 /MWCNTs composite are matched well with the
crystal planes of (0 0 1), (1 1 1) and (0 2 0) in MnO2 (JCPDS 42-1317,
MnO2 ) respectively. This result indicates that birnessite-type MnO2
has been successfully incorporated on the MnO2 /MWCNTs com-
posites [15,16]. Additionally, it is noted that with the increasing of
the MnO2 contents, the peak at 2 = 44◦ is gradually decreasing.
It also indicates the successful formation of MnO2 /MWCNTs
composite.
SEM was used to monitor the morphological characteristics of
the MnO2 /MWCNTs composite. Fig. 2 presents the SEM images
of the MWCNTs before and after MnO2 deposition. From Fig. 2,
it can be seen that the unmodified MWCNTs are in the form
of the small bundles with a diameter of 30–50 nm. Upon reac-
tion with KMnO4 , the MWCNTs are uniformly decorated with
the particles on their surfaces, as shown in Fig. 2b–d, indicating
the deposited MnO2 on the MWCNTs are in the form of parti-
cles. However, it is noted that there is no obvious change of the
surface morphology of the MWCNTs upon the incorporation of
MnO2 particle. Also, with the increasing of the contents of MnO2
from 25% to 75%, the surface coverage of the MnO2 particles is
enhanced.
3.2. Wettability of the anode surface
Water contact angle measurements were used to inves-
tigate the wettability of the MnO2 /MWCNTs modified anode
surface [18,19]. In Fig. 3, photographs are shown of the water
droplets on a variety of the different modified electrode sur-
faces. Compared to that of the bare PG electrode (145◦ ) and the
MWCNTs modified electrode (137◦ ), the contact angles of the
MnO2 /MWCNTs modified electrode surfaces are greatly decreased
(49◦ for 25% MnO2 /MWCNTs, 55◦ for 50%MnO2 /MWCNTs, 65◦
for 75%MnO2 /MWCNTs). This suggests that the modification
method can lead to the formation of a hydrophilic surface. It
should result from the hydrophilic functional group (i.e., OH)
introduced by the modification layer of MnO2 on MWCNTs.
The MWCNTs surface may have a little amount of hydrophilic
oxidative group [20], but from Fig. 3, its contact angles still
86 Y. Fu et al. / Applied Surface Science 317 (2014) 84–89

Fig. 2. SEM images of MWCNTs (a) and MnO2/MWCNTs with different MnO2 contents: (b) 25%, (c) 50% and (d) 75%.

is much higher that the MnO2 modified anodes do. Also, the
contact angles increase gradually with the increasing of the
MnO2 contents (Fig. 3b–d). Hence, the wettability changes can
be attributed to the introduced MnO2 , not to the preparation
process.
3.3. Kinetic activity of different anodes
Tafel plots were used to evaluate the kinetic activity of the
different modified anodes. In Fig. 4, it can be seen that after
initial steep current increases, all curves become linear. The

Fig. 3. Images of contact angle measurement, (a)–(e) as-prepared MnO2 /MWCNTs anodes having the content of MnO2 of 0%, 25%, 50% and 75% respectively, (d) PG anode.
 Y. Fu et al. / Applied Surface Science 317 (2014) 84–89 87

Fig. 4. Tafel plots of different anodes.

exchange current density, i0 , is obtained by extrapolation to

 = 0 of a linear regression (R2 > 0.98) between  = 60–80 mV. The
value of i0 of the different anodes is 3.1 × 10−5 A cm−2 (MWC-
NTs), 7.9 × 10−5 A cm−2 (MnO2 (25%)/MWCNTs), 3.2 × 10−3 A cm−2
(MnO2 (50%)/MWCNTs), 2.5 × 10−4 A cm−2 (MnO2 (75%)/MWCNTs)
and 1.3 × 10−5 A cm−2 (PG), respectively. Compared with that of the
bare PG, the exchange current density of the MnO2 (50%)/MWCNTs
anode has a 246.1-fold increase, which indicates that the activation
energy of biochemical reactions on such modified electrode surface
has been greatly reduced.

3.4. Electric performance of the BMFCs

The performance of the BMFCs equipped with the MWCNTs

(BMFC-A), MnO2 (25%)/MWCNTs (BMFC-B), MnO2 (50%)/MWCNTs
(BMFC-C), MnO2 (75%)/MWCNTs (BMFC-D) and PG anode (BMFC-
E) are evaluated by measuring the power density (Fig. 5A), the
anode and cathode polarization (Fig. 5B), and the output current
during operation (Fig. 5C), respectively. The maximum power den-
sity outputs with variable external resistance of the BMFCs were
109.1 mW m−2 (BMFC-C), 52.1 mW m−2 (BMFC-B), 35.2 mW m−2
(BMFC-D), 18.1 mW m−2 (BMFC-A) and BMFC-E (9.2 mW m−2 ),
respectively. The results obtained from Fig. 4B show that the
anode is the main limiting factor in these BMFCs. In BMFC-
C, for instance, with increasing the current densities of in the
range of 0–450 mA m−2 , the cathode potential drop from 298
to 242 mV, whereas the anode potential increase rapidly from
−485 to −398 mV. The MnO2 /MWCNTs nanocomposites signifi-
cantly improve the performance of BMFCs, as evidenced from the
decreased slope of anode polarization curves.
To further obtain cell current output for a long-term, the BMFCs
are connected to an external resistance of 500 . As can be seen
from Fig. 5C, a steady current is generated on all the cells on the
4th day after closing the circuit. During 30 days, the maximum
steady current generate by BMFC-C was 1.2 mA, which is much
higher than that of BMFC-A (0.5 mA), BMFC-B (0.9 mA), BMFC-D Fig. 5. Performance of the BMFCs with the MWCNTs (BMFC-A), MnO2 (25%)/MWC-
NTs (BMFC-B), MnO2 (50%)/MWCNTs (BMFC-C), MnO2 (75%)/MWCNTs (BMFC-D)
(0.7 mA) and BMFC-E (0.3 mA). Therefore, the above results indi-
and PG anode (BMFC-E): (A) power density, (B) anode and cathode polarization
cate that the nanocomposites have a better electrical performance curves and (C) current generation with a 500  load.
in the BMFCs which is highly attributed to MnO2 content.
Table 1 summarizes the results of the laboratory evaluation
of the modified anodes and the cells. Apparently, the MnO2 much lower conductivity, which will greatly hinder the electron
(50%)/MWCNTs anode shows the highest electrochemical perfor- transfer ratio and result in the lower kinetic activity and cell output.
mance. On one hand, its higher content will be beneficial to increase Therefore, 50% content of MnO2 presents its best result.
the hydrophilic property (wettability) (Fig. 3) and could enhance A synergetic mechanism (Fig. 6) is proposed for these positive
more attached bacteria, maintaining more electrons and higher effects of the MnO2 /MWCNTs nanocomposites as follows: (i) Bet-
kinetic activity; however, on the other hand, when the excessive ter wettability of the MnO2 /MWCNTs composite is favorable for the
MnO2 is deposited, the resistance is greatly increased due to its bigger contact area and growth of the attached microorganism and
88 Y. Fu et al. / Applied Surface Science 317 (2014) 84–89

Table 1
Summary of different anodes and cells performance.

Anode MWCNTs MnO2 (25%)/MWCNTs MnO2 (50%)/MWCNTs MnO2 (75%)/MWCNTs PG

Contact angle (◦ ) 137 49 55 65 145

Kinetic activitya (KA) 2.4 6.1 246.1 19.2 1
Maximum power density (mW m−2 ) 18.1 52.1 109.1 35.2 9.2
Steady current generation (mA) 0.5 0.9 1.2 0.7 0.3
a
KA was calculated by the ratio between other anodes and PG, obtained from Tafel plots in Fig. 4

Fig. 6. Synergetic enhanced mechanism to explain its excellent performance with the MnO2 /MWCNTs anode in the BMFCs.

its porous network microstructure favorable for the enhancement
of mass transport. (ii) The deposition of MnO2 upon the MWCNTs
can facilitate the Mn-related bacteria enrichment and contribute
significantly to provide more electrons [21]. (iii) Mn(IV) is func-
tioning as a mediator for the electron transfer [22]; Mn(II)/Mn(VI)
couple acts as a shuttle to transfer electron from Mn-related bacte-
ria to the anode. On anodic surface, they may have the following
redox mediator reactions occurred. In Eq. (1), under microbial reac-
tion, there would be some mediator products (Mn3+ compounds,
for example, MnOOH, MnOx ) and final product (Mn2+ ) formed.
MNOOH or MnOx
MnO2 + 4H+ + 2e −→ Mn2+ + 4H2 O
Cytochrome C and microbial action
MNOOH or MnOx
Mn2+ − 2e + 2H2 O −→ Mn4+ + 4OH− (Mn(OH)4 )
MWCNTS/Anode
electrons by oxygen reduction (O2 + 4e + H+ = H2 O, EO2 /H2 O =
+1.229 V or O2 + 4e + H2 O = 4OH− , EO /OH− = +0.41 V), there exists
2
a big driving force to make the Mn2+ lose electrons and deliver
them to anode and finally to the cathode through outer circuit. In
brief, due to the microbial action, a electron shuttle of Mn4+ /Mn2+
is formed in the anodic interface between modification layer and
bacteria biofilm to improve the kinetic activity (Fig. 6).
In all, these factors could be synergetic to increase the kinetic
activity of the anode and accelerate the rate of electron transfer. In
a word, with the MWCNTs support, the electron transfer and the
mass transport efficiencies on the modified electrode surfaces can
(1) be greatly enhanced. We would think that it is these synergy effects
between MnO2 and MWCNTs on the anode surface that makes the
(2) BMFCs achieve excellent performance.

Mn(OH)4 −→MnO2 + 2H2 O (3)

H+ 4. Conclusions

Here, the redox potential of reaction (1), EMnO
2 /Mn
0.7–1.23 V, according to the different pH [23]. Due to the micro-
bial metabolism producing H+ , anodic surface should be weak
acidic condition; therefore, its redox potential should be 0.7 V
(pH 6–7). Because the redox potential of cytochrom C (a kind
of electron transfer mediator) in bacterial membrane is about
0.2–0.3 mV, MnO2 will capture electrons from it. In reaction (2),
the identical mediator products (Mn3+ compounds) will also exist
and the potential EMn2+ /Mn3+ is −0.1 V or so. Because the cath-
ode in cell circuit has very high positive potential and exhaust
2+ is In conclusion, the MnO2 /MWCNTs nanocomposites are fab-
ricated and utilized as high-performance and low-cost anode
materials in the BMFCs. The BMFCs with the MnO2 (50%)/MWC-
NTs anode delivered a maximum power output of 109.1 mW m−2
and a maximum steady current of 1.2 mA, which are much higher
than that of other anodes. Benefiting from the surface wettability,
three-dimensional electronic conductivity of MWCNTs and Mn-
related bacteria enrichment, the MnO2 /MWCNTs nanocomposites
show higher kinetic activity and power output. An electron trans-
fer synergetic mechanism of Mn ions and their redox reactions in
 Y. Fu et al. / Applied Surface Science 317 (2014) 84–89
the interface between modification layer of MnO2 and bacterial
biofilm is presented for the explanation of its good electrochemical
performance.
Acknowledgments
This study was supported by the Key Project of Nature Science
Fund of Shandong Province, China (ZR2011BZ008), and the Special
Fund of Marine Renewable Energy from State Ocean Bureau, China
(GHME2011GD04).
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