J. Ocean Univ.

China (Oceanic and Coastal Sea Research)

DOI 10.1007/s11802-015-2588-y
ISSN 1672-5182, 2015 14 (4): 663-668
http://www.ouc.edu.cn/xbywb/
E-mail:xbywb@ouc.edu.cn

Carbon Foam Anode Modified by Urea and Its Higher

Electrochemical Performance in Marine Benthic
Microbial Fuel Cell
FU Yubin1),*, LU Zhikai1), 2), ZAI Xuerong3), and WANG Jian1)

1) Institute of Materials Science and Engineering, Ocean University of China, Qingdao 266100, P. R. China
2) China Lucky Group Corporation, Baoding 071000, P. R. China
3) College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, P. R. China

(Received February 12, 2014; revised February 6, 2015; accepted March 2, 2015)
Ocean University of China, Science Press and Springer-Verlag Berlin Heidelberg 2015

Abstract Electrode materials have an important effect on the property of microbial fuel cell (MFC). Carbon foam is utilized as an
anode and further modified by urea to improve its performance in marine benthic microbial fuel cell (BMFC) with higher voltage and
output power. The electrochemical properties of plain carbon foam (PC) and urea-modified carbon foam (UC) are measured respec-
tively. Results show that the UC obtains better wettability after its modification and higher anti-polarization ability than the PC. A
novel phenomenon has been found that the electrical potential of the modified UC anode is nearly 100 mV lower than that of the PC,
reaching 570 10 mV (vs. SCE), and that it also has a much higher electron transfer kinetic activity, reaching 9399.4 mW m2, which
is 566.2-fold higher than that from plain graphite anode (PG). The fuel cell containing the UC anode has the maximum power density
(256.0 mW m2) among the three different BMFCs. Urea would enhance the bacteria biofilm formation with a more diverse microbial
community and maintain more electrons, leading to a lower anodic redox potential and higher power output. The paper primarily
analyzes why the electrical potential of the modified anode becomes much lower than that of others after urea modification. These
results can be utilized to construct a novel BMFC with higher output power and to design the conditioner of voltage booster with a
higher conversion ratio. Finally, the carbon foam with a bigger pore size would be a potential anodic material in conventional MFC.

Key words marine benthic microbial fuel cell; carbon foam anode; urea modification; low anode potential; high kinetic activity;
high output voltage

duces relatively low levels of power density, prohibiting

1 Introduction
Microbial fuel cell (MFC) is a device that uses bacteria
to catalyze the conversion of organic matter into electric-
ity (Ashley and Kelly, 2010). Substrate is oxidized by
bacteria generating electrons and protons at the anode.
Electrons are transferred through an external circuit while
the protons diffuse through the solution to the cathode,
where electrons combine with protons and oxygen to
form water (Rabaey and Verstraete, 2005). Marine ben-
thic microbial fuel cell (BMFC) is a field-deployable and
uniquely configured microbial fuel cell that relies on the
natural redox processes in aqueous sediments (Reimers
et al., 2006). Its anode is imbedded in the sediment and
cathode is planted in overlying water. Meanwhile, the
anode is connected by an external circuit to the cathode.
The cells are under development as long-term power
sources for autonomous sensors and acoustic communica-
tion devices deployed in shallow or deep sea environ-
ments (Reimers, 2001; Alberte, 2005). However, it pro-
* Corresponding author. E-mail: ffyybb@ouc.edu.cn
its widespread application. Researchers have used various
methods, such as selection of high efficient anode mate-
rial or its modification to increase power density (Wei,
2011; Zhou, 2011).
A variety of anodic materials have been used in the
MFCs, including plain graphite, carbon paper, carbon
cloth and carbon felt. It appears to be a general trend that
the higher surface area anodic material, the higher power
output (Chaudhuri and Lovley, 2003). Carbon foam has
an exceptionally high void volume (97%), a large pore
size ( 2 mm), and low diffusion resistance. Thus, it is an
ideal anode material in the BMFC. On the other hand, the
anode modification is one of the effective ways to im-
prove the output power. For example, ammonia gas has
been used to modify carbon mesh and make the cell
power density reach 1015 mW m2 due to the introduction
of N-containing groups; carbon mesh has a high N/C ratio
to improve electron transfer (Wang et al., 2009). Urea
molecule has a higher content of the element N. Further
increasing the amount of N-containing group can yield
higher power output. Therefore, urea-modified anode is
fabricated in the present paper.
664 FU et al. / J. Ocean Univ. China (Oceanic and Coastal Sea Research) 2015 14: 663-668
A novel phenomenon is found that the modified anode
potential is 570 10 mV (vs. SCE), 100 mV lower than
the plain (440 10 mV, vs. SCE) and the output voltage
of the modified BMFC is 870 15 mV. This result has a
significant meaning for the device design of a voltage
booster. At present, the main limitations of the BMFCs to
drive small monitor or equipment to work for a long-term
service on ocean floor are their low power and output
voltage (Zhang and Angelidaki, 2012). So we need to
design a voltage booster device to improve output voltage
and satisfy the voltage requirement for driving marine
electronic instruments. In the paper, higher cell output
voltage will be beneficial to design the booster condi-
tioner with a higher power conversion ratio.
2 Experimental Section
2.1 Materials
Carbon foam (pore diameter > 2 mm) was purchased
from Qingdao Gaotai New Material Co., Ltd, China
(shown in Fig.1a). Urea (purity > 99.0) from Tianjin Gu-
angcheng Chemical Co., Ltd. Graphite powder (500 mesh)
from Qingdao Tianhe Graphite Co., Ltd. Graphite block
and plate from Qingdao Duratight Carbon Co., Ltd. The
materials were all directly used without further treatment.
Natural sediment and seawater were then collected from
the Jiaozhou Bay in Qingdao, China (at 3610.3N,
12018.1E).
2.2 Urea-Modified Anode Preparation
Three types of anodes were employed in the BMFCs.
All of the anodes only had one work surface (2 cm 2 cm)
and the other five surfaces were coated by epoxy resin.
These three anodes were called plain graphite block (PG),
plain carbon foam (PC) and urea-modified carbon foam
Fig.1 Carbon foam anode (a-1), carbon plate (a-2) and the BMFC configuration (b).
2.4 Analytical Measurements
XRD patterns were obtained from Macscience-M18
XHF Instrument. Water contact angle was measured by a
(UC) respectively. The UC was prepared according to the
following procedure: 30 g of urea and 15 g of graphite
powder were mixed and heated for 5 min 10 min in the
temperature range 120 130, then PC was soaked in the
melted urea mixture for 1 min and dried at the room tem-
perature for 12 h. The modified anodes characterized by
X-ray diffraction (XRD) and water contact angle, were
accurately weighed by electronic analytical balance to
calculate the mass fraction of urea.
Carbon foam is a porous material and it is necessary to
design a joint point to protect the lead wire from the cor-
rosion of seawater. We used a glue to adhere carbon foam
to a graphite plate and then sintered them under a high
temperature (more than 2000) in the N2 atmosphere to
form a unity material. After that, copper lead wire was put
into a small hole in the graphite plate by using conductive
glue to protect the lead wire. Finally, a carbon foam an-
ode was formed (Fig.1a).
2.3 BMFC Design and Configuration
Three BMFCs were constructed with the designed
anodes (UC, PC, PG) and cathode. Cathode was then
made of a big graphite plate (length 25 cm, width 20 cm,
thickness 1.2 cm) to ensure that it has a great larger area
than the anode. The PG, PC and UC as working electrodes
were respectively imbedded in sediment; meanwhile the
graphite plate and a reference electrode (saturated calo-
mel electrode SCE) were positioned in the overlying
seawater. The depth of the marine sediment was 20 cm,
seawater 15 cm and the distance between cathode and
anode was 15 cm (Fig.1b). The cells constructed by the
UC, PC and PG anode were called BMFC-UC, BMFC-
PC and BMFC-PG respectively. Three parallel experi-
ments were conducted in an identical configuration to
obtain average results.
contact angle meter (KRUSS DSA100 Germany). Cath-
ode potentials were directly measured by the SCE and the
anode potentials were calculated by subtracting the cell
voltage from cathode potentials (Song and Jiang, 2011).
 FU et al. / J. Ocean Univ. China (Oceanic and Coastal Sea Research) 2015 14: 663-668 665

Voltage and current produced from the BMFCs during the
experiments were recorded at 15 min intervals using digi-
tal multimeters (Shenzhen Huayi Instrument Co., Ltd).
Power (P) was calculated according to P = IU, where U is
voltage and I current. Current and power were normalized
to the geometric surface area of the anode when calculat-
ing current and power densities (Ryckelynck et al., 2005).
The maximum power density of the BMFC was estab-
lished from polarization curve using a variable resistor
box (from 10000 to 0 , ZX-21, Shanghai Precision &
Scientific Instrument Co., LTD). Tafel plots (log [ex-
change current density i0] versus overpotential ) were
recorded for each anode by sweeping voltage at 10 mV s1
from = 0 200 mV, where = 0 is the OCP of the anode
vs. SCE (Lowy et al., 2006). The exchange current den-
sity (i0) of each anode was determined from Tafel plots by
extrapolation to = 0 of a linear regression between =
75 150 mV. It must be chosen at a low overpotential
range so that the i0 values will depend on the charge-lim-
ited electrochemical process and the effect of mass trans-
fer on anodic potential can be negligible. The potential
sweep curves (sweeping voltage at 1 mV s1 from the OCP
to 200 mV) of different anodes were obtained from a
Model LK2005A Electrochemical Workstation (Tianjin
Lanlike Co., Ltd). All of the measurements of electro-
chemical behavior were conducted in a three-electrode
configuration: the anode imbedded in the sediment as a
working electrode, the cathode as a counter and the SCE
as a reference electrode.
wettability is. Good wettability can improve the adhesion
of microorganism and accelerate electron production be-
cause many biochemical reactions undergo on the hydro-
philic surface.
3.2 Electrochemical Behavior of Different Anodes
Anode polarization curves are shown in Fig.3a (each
data point is an average value from three times of meas-
urement, error 10 mV). There is a sharper drop slope of
the PG than the PC and UC do. It indicates that the PC
and UC have better anti-polarization ability. Bigger po-
rosity and larger surface area provide more space for mi-
croorganism to reside in, which in turn produces more
electrons for transfer (Scott et al., 2007). After modifica-
tion, urea may serve as a new fuel substrate to satisfy the
demand of attached bacteria, or form hydrogen bonding
with peptide bonds in bacterial cytochromes, which can
remove the barrier for electron transfer (Zheng et al.,
2007). Therefore, the UC has the best anti-polarization
ability among them.

3 Results and Discussion

3.1 Modified Anode and Characterization
XRD patterns show that several sharp peaks exist after
urea modification (see the attached information), indicat-
ing that urea is still in the crystal state. Weight difference
calculation before and after modification shows that urea
has the mass percentage of 43.6% in the anode.
Fig.2 shows contact angle images and their sizes in
three parallel experiments are shown in Table 1. The
value of the modified anode reduces by 49.1 versus the
plain anode. The decrease in the contact angle is caused
by the polarity functional groups in urea. Studies have
shown that the contact angle stands for the wettability and
it is closely related to the electrochemical reaction (Suski
et al., 1999). The lower the contact angle is, the better the

Fig.3 Anode polarization curves (a) and potential sweep

curves of different anodes (b).

Fig.2 Images of the contact angle, PC (a) and UC (b). Fig.3b shows the potential sweep curves of the differ-
ent anodes. It is a useful method to evaluate the anodic
Table 1 Contact angles of the plain and modified anodes
electrochemical property. The UC has the highest value of
Anodes 1 2 3 Average values the anodic current density and the PG the least value. The
PC 88.5 90.5 92.0 90.3 5 UC curve has a current peak 1100 mA m2 at 50 mV and
UC 39.5 41.5 42.5 41.2 5 then it decreases and the current finally keeps steady after
666 FU et al. / J. Ocean Univ. China (Oceanic and Coastal Sea Research) 2015 14: 663-668
50 mV. It could reasonably be speculated that the urea on
the anode surface may be serve as a substrate to donate
more electrons than other anodes do at 50 mV, but then
the mass diffusion resistance on the anode surface limits
the current to increase further. Finally it reaches a balance
and maintains a higher current value than the PG and PC.
Anode kinetic activity stands for the electron transfer
ratio on its surface and means the anodic exchange cur-
rent density. It is a key factor to increase the current and
power density of the BMFC. Tafel plots (Fig.4) show that
all curves become linear after an initial steep current in-
creasing. According to the Tafel equation ( = a + b log |i|),
the i0 values (exchange current density) obtained from
these plots are 16.6 mA m2 (PG), 125.9 mA m2 (PC) and
9399.4 mA m2 (UC) respectively. The i0 value of UC is
almost three orders of magnitude higher than the PG, in-
dicating that the activation energy of the biochemical
reactions on the UC reduces greatly.
Fig.4 Tafel plots of different anodes.
3.3 BMFC Performance with Different Anodes
The BMFCs with different anodes show the variations
of output voltage in Fig.5a (each data point is an average
value from three times of measurement). The voltage of
BMFC-UC is 870 15 mV, BMFC-PC 770 15 mV and
BMFC-PG 740 15 mV. Though the UC curve has a mild
slope, it is close to be linear, indicating that it has a steady
internal resistance and its activation and mass-transfer
losses do not increase after discharge. The steep decrease
in voltage at low current density suggests that the
BMFC-PG has a high activation loss (Martins et al.,
2010). The maximum power densities of the three differ-
ent BMFCs are 256.0 mA m2 for UC, 151.3 mA m2 PC,
19.6 mA m2 PG respectively. The UC power is 13-fold
higher than that of PG, and nearly 1.7-fold higher than
that of PC.
Compared with the literature (Wang et al., 2009), the
UC power in the paper is much lower than the cell power
(1015 mA m2) obtained by Wang et al. (2009), where the
anode was modified by ammonia gas. The large structure
difference in microbial fuel cells is another important
reason for the big difference in power output. The BMFC
directly uses natural seawater and sediment (sea mud) to
construct fuel cell, in which case it can not be stirred or
air-pumped. However, in the conventional MFC, the sin-
gle and high effective cultured bacterial species is gener-
ally utilized and cell structure can be artificially stirred or
air-pumped to increase its power output.
Anode stability is a significant parameter for the BMFC
application. The long-term discharge of the BMFC-UC in
Fig.5b shows that the initial 20 d are developing period
and it becomes steady in the following time. This ex-
periment has operated for six months. The UC anode po-
tential can still be sustained at 570 10 mV and the
voltage at 870 15 mV. This result illustrates that the UC
has a better stability in sediment and maintains a higher
output voltage than the PC and PG do.
Fig.5 Cell polarization plots and power density curves of
three BMFCs (a), UC long-term steady performance (b).
The result also indicates that the modified anodes with
different urea contents have the identical electrochemical
behavior, but higher contents of urea can make the cell
have a long-lasting discharging time with higher voltage.
3.4 Electro-Catalytic Activity Analysis of the Modi-
fied Anode
The results of the three types of anodes are summarized
in Table 2. The anode electrical potentials are 440 10
mV (PG), 470 10 mV (PC) and 570 10 mV (UC)
respectively. The UC potential is lower by nearly 100 mV
and its cell voltage reaches 870 15 mV. Its kinetic activ-
ity is 566.2-fold higher than that of PG and 74.5-fold
higher than that of PC. The anode potential is one of the
determining elements for the collection of energy from
the microorganisms and it can regulate both the activity
 FU et al. / J. Ocean Univ. China (Oceanic and Coastal Sea Research) 2015 14: 663-668 667

and growth of bacteria to sustain enhanced current and 6 V, 12 V, etc. However, lower cell voltage leads to lower
power generation (Zhou et al., 2011). In a word, the UC power conversion ratio of the booster device. Thus,
electrical potential is reduced and its cell voltage in- higher cell output voltage will improve the power conver-
creases after modification. This is a novel phenomenon sion ratio of the booster device. This study provides a
reported for the first time. new way for constructing higher voltage BMFCs by de-
BMFC as a power source for driving marine instrument signing novel voltage booster conditioner with higher
needs to design voltage booster device from 0.5 V to 5 V, ratio.
Table 2 Electro-catalytic activity of three different anodes
Cell voltage Maximum power density Exchange current density
Anodes OCP (mV, vs. SCE) Anodic kinetic activity
(mV) (mW m2) (mA m2)
PG 440 10 740 15 19.6 10 16.6 1.0
PC 47010 770 15 151.3 10 125.9 7.6
UC 57010 870 15 256.0 10 9399.4 566.2

A possible mechanism of the BMFC with urea- modi-
fied anode is presented in Fig.6. Song et al. (2012) re-
ported that the output voltage increases by 30 mV due to
increase of Fe (III) in sediment. Zhang et al. (2011) dem-
onstrated that different substrates lead to different micro-
bial community enrichment. Thus, it could be reasonably
speculated that besides the traditional microbial oxidation
reaction, UC selects a new microbial community with
lower redox potential that can catalyze oxidation of urea
and generate electrons (new bacterial species on modified
anode surface as seen in Fig.6). This process may be
beneficial for nitrogen cycle in the environment; equa-
tions I and II particularly show the nitrogen cycle process
(AQDS is a widely existing product of humus respiration
in anaerobic sediment (Wu et al., 2009)). However, it
needs further detailed research on the attached bacteria to
explain why the electrical potential of the modified anode
decreases.
4AQDS + 3H2O + NH2+ NO3 + 3H+ + 4AHQDS (I)
2NO3+ 2H+ + 5AHQDS 5AQDS + 6H2O + N2 (II)
In the reaction (I), the urea acts as a reduction agent,
which may cause the anodic electrical potential to de-
crease.

Fig.6 Schematic representation of the mechanism of the BMFC with modified anode. Darker color in the modified anode
stands for a lower potential and the rod and sphere on its surface means much more different bacteria than on the plain
electrode due to the urea.

(870 15 mV). The power densities of the three different

4 Conclusions
Carbon foam modified by urea has been used as a
novel anode for increasing the N/C ratio to improve an-
odic performance in marine benthic microbial fuel cell. A
novel characteristic of the modified anode is that it has a
lower potential (570 10 mV) than that of the plain
graphite and the fuel cell obtains a higher output voltage
fuel cells are 256.0 mW m2 (modified carbon foam),
151.3 mW m2 (carbon foam) and 19.60 mW m2 (plain
graphite) respectively. The higher exchange current den-
sity and higher kinetic activity of the urea-modified car-
bon foam have also been achieved. Urea as a microbial
nitrogen source can promote the bacteria biofilm forma-
tion with a diversity of communities and produce more
electrons leading to a higher power. Finally, the novel
668 FU et al. / J. Ocean Univ. China (Oceanic and Coastal Sea Research) 2015 14: 663-668
urea-modified anode offers good prospects for application
in the marine BMFCs or other MFCs.
Acknowledgements
This work is supported by the Key Project of Natural
Science Fund of Shandong Province, China (ZR2011
BZ008), and the Special Fund of Marine Renewable En-
ergy from State Ocean Bureau, China (GHME2011GD
04).
Attached Information
XRD patterns of urea before and after melting. Urea
peaks have a good consistence with its standard card.
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