Technical Note

Received: 25 April 2013 Revised: 11 June 2013 Accepted article published: 20 June 2013 Published online in Wiley Online Library: 16 July 2013

(wileyonlinelibrary.com) DOI 10.1002/jctb.4156

Copper anode corrosion affects power

generation in microbial fuel cells
Xiuping Zhu and Bruce E. Logan∗

Abstract
Non-corrosive, carbon-based materials are usually used as anodes in microbial fuel cells (MFCs). In some cases, however,
metals have been used that can corrode (e.g. copper) or that are corrosion resistant (e.g. stainless steel, SS). Corrosion could
increase current through galvanic (abiotic) current production or by increasing exposed surface area, or decrease current due
to generation of toxic products from corrosion. In order to directly examine the effects of using corrodible metal anodes, MFCs
with Cu were compared with reactors using SS and carbon cloth anodes. MFCs with Cu anodes initially showed high current
generation similar to abiotic controls, but subsequently they produced little power (2 mW m-2 ). Higher power was produced
with microbes using SS (12 mW m-2 ) or carbon cloth (880 mW m-2 ) anodes, with no power generated by abiotic controls. These
results demonstrate that copper is an unsuitable anode material, due to corrosion and likely copper toxicity to microorganisms.

c 2013 Society of Chemical Industry

Keywords: copper anode; stainless steel anode; carbon cloth anode; microbial fuel cell

INTRODUCTION resistances minimized,20 or by an analysis of the maximum biofilm

Microbial fuel cells (MFCs), which use bacteria to oxidize organic
wastes and simultaneously generate electricity, are promising for
energy recovery from wastewater treatment.1 – 3 Exoelectrogenic
bacteria on the anode can oxidize organic compounds to CO2 , and
generate electrons and protons. The electrons are transferred to
the cathode through an external circuit while the protons diffuse
to the cathode through the solution. At the cathode, typically,
oxygen is used as the electron acceptor, producing water from the
reaction with electrons and protons.
The anode material is one of several critical factors that can
affect the performance of an MFC. Various materials have been
examined as anodes in MFCs, such as graphite,4 carbon cloth,5
carbon fiber,6 activated carbon,7 stainless steel (SS),8 copper,9 and
nanostructured materials.10,11 It is generally believed that non-
corrosive, carbon-based materials are most suitable for bacteria
growth, especially for highly porous structures such as cloth,
felt and graphite fiber brushes.12 However, the use of corrosion-
resistant, flat SS for the anode has been shown to produce current
densities higher than that of graphite plates in bioelectrochemical
tests.13
Corrosion of a metal anode can affect current generation in
several ways. Current could be increased due to abiotic current
generation from metal corrosion, or from increases in surface area.
The standard potential for copper corrosion (Cu
Cu2+ + 2e – )
is 0.340 V vs NHE in aqueous solutions at 25◦ C,14 compared with
–0.3 V for acetate oxidation. Alternatively, current generated by
bacteria could be negatively affected by the generation of toxic
metals. In one study, a very high power density of 40 W m –2
for a MFC was generated when a copper anode was used.15 This
power density is remarkable as it remains considerably higher
(10–40 times) than other values reported in the literature.16 – 19
In addition, these power densities exceed those thought to be
kinetics.21,22 Copper is an interesting choice as an anode because
it can corrode, either increasing current (and power) or decreasing
current due to the toxicity of copper ions to microorganisms.
In order to determine what the effect of a copper anode would
be on current generation in a MFC, we examined power generation
using Cu anodes in MFCs and in similar abiotic reactors. Power
production in MFCs was compared with that obtained with anodes
made from corrosion-resistant SS or carbon cloth under otherwise
identical conditions.
EXPERIMENTAL
MFCs (duplicates) were constructed from a solid cube of Lexan
with a cylindrical chamber (2 cm long and 3 cm in diameter).
Anodes were made from copper mesh (50 × 50, McMaster-Carr),
SS mesh (50 × 50, McMaster-Carr), or carbon cloth (Fuel Cell Earth
LLC) (all 3 cm diameter, 7 cm2 projected area), and fixed at one end
of the chamber. An air cathode of the same size, placed at the other
end, was made from carbon cloth and four polytetrafluoroethylene
diffusion layers on the air-side, and a catalyst layer of 0.5 mg Pt cm –2
and a Nafion binder on the water side.23 MFCs were inoculated
using effluent from other MFCs. The growth medium contained
(per L): 1 g sodium acetate, 4.28 g Na2 HPO4 , 2.45 g NaH2 PO4 ·H2 O,
0.31 g NH4 Cl, 0.13 KCl, 12.5 mL minerals, and 5 mL vitamins.24
MFCs were acclimated with a 1000
external resistor for 54 days,
and then with a 10
external resistor for another 32 days. Reactors
were operated in batch mode and solutions were replaced in 1 or
2 days. A multimeter (Model 2700, Keithley Instruments) was used
∗
Correspondence to: B.E. Logan, Department of Civil and Environmental
Engineering, Penn State University, USA. E-mail: blogan@psu.edu
471

possible by anodic biofilms based on an analysis with all internal Department of Civil and Environmental Engineering, Penn State University, USA

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 www.soci.org X Zhu, B E Logan

to measure the voltage (U, mV) over the external resistor (R,
),
with the current (I, mA) calculated as I = U/R.
Polarization and power density curves were obtained by linear
sweep voltammetry (LSV) with a potentiostat (VMP3, BioLogic) at
a scan rate of 0.2 mV s –1 from open circuit voltage (OCV) to short
circuit (0 V vs. the cathode potential).19 The Ag/AgCl reference
electrode (BASi) was placed in the middle of the MFC chamber
to obtain anode and cathode potentials (reported versus Ag/AgCl
electrode, +210 mV vs. a standard hydrogen electrode). Current
and power densities were normalized to the projected surface area
of one side of a single electrode (7 cm2 ). Cu2+ concentration in
the effluent was detected using atomic absorption flame emission
spectrophotometer (AA-6601F, Shimadu).

RESULTS AND DISCUSSION

MFCs (previously inoculated with bacteria) that had Cu anodes
immediately generated current when the circuit was connected
(1000
), which was very unusual compared with carbon-based
anodes (Fig. 1(a)). The maximum current for the first cycle with the
Cu anode was 0.18 ± 0.02 mA. This decreased to approximately
0.02 mA for the second cycle, and then stabilized at only 0.003 mA
over successive cycles. Additional inoculation of the reactor with
microbial suspensions did not increase the current above 0.003
mA. Decreasing the external resistance to 10
did not improve
current production.
MFCs containing SS or carbon cloth anodes that were inoculated
with bacteria initially generated little current, but the current
gradually increased over time to 0.03 ± 0.01 mA for SS anodes (Fig.
1(b)) and 0.50 ± 0.05 mA for carbon cloth anodes (Fig. 1(c)). When
the external resistance was changed to 10
, the current in MFCs
with carbon cloth anodes immediately increased to 3.8 ± 0.3 mA
(Fig. 1(c)).
Polarization data were obtained when the current generation
of all MFCs were reproducible over several cycles (Fig. 2). The
maximum power densities when acclimated to a 1000
resistor
were 2 ± 0.3 mW m-2 for MFCs with Cu anodes, 12 ± 3 mW m-2
with SS anodes and 880 ± 20 mW m-2 with carbon cloth anodes.
There were no consistent changes in maximum power densities
when the reactors were acclimated to 10
, with relatively small
increases observed for carbon and Cu anodes, and a slightly larger Figure 1. Current generation of MFCs with (a) Cu, (b) SS, or (c) carbon cloth
anodes with 1000
or 10
external resistors.
decrease for SS anodes. For MFCs with carbon cloth anodes, power
overshoot in the high current region disappeared after acclimation
to a low resistance (10
).19,25 and power were produced with Cu anodes. The maximum current
The substantially higher power density with the carbon cloth achieved without microbial inoculation was 0.30 ± 0.05 mA for
anode was due in part to the higher specific surface area of cloth the first cycle (10
), decreasing to 0.003 ± 0.001 mA with a
compared with SS mesh. The initial high current produced from maximum power density of 2 ± 0.5 mW m-2 . These current and
the Cu anode MFCs suggests a chemical (galvanic) current was power densities were similar to those obtained in MFCs with Cu
generated, as there was insufficient time for microorganisms to anodes that were inoculated with micoorganisms. Additionally,
grow on the anode and generate current. A typical acclimation elevated concentrations of Cu2+ (0.5–1 mg L-1 ) were detected in
time of several fed-batch cycles was needed for biological current the effluents from both the abiotic and biotic MFCs with Cu anodes.
generation, as observed with the SS or carbon cloth anodes (Fig. These results confirmed that bacterial growth was inhibited in tests
1(b) and 1(c)). The lack of appreciable current generation in all with Cu anodes, probably due to the toxicity of the solubilized
but the first cycle with the Cu anodes suggests that corrosion copper from electrode corrosion.
led to production of soluble copper, which is known to be These results lead us to seriously question the validity of a
toxic to microorganisms, which inhibited current generation by previous report of very high power density in an MFC with a Cu
microorganisms in these reactors. anode.15 A power density of 40 W m-2 must either be a calculation
In order to confirm that current generation in the MFCs with error, or due solely to copper corrosion with the solution used in the
Cu anodes was due to copper corrosion, abiotic controls were tests. Several factors could have served to enhance Cu corrosion,
performed with all three types of electrodes under otherwise such as cleaning the Cu anode periodically and replacing it every
identical conditions (Fig. 3). No current or power was generated 12 days to maintain corrosive conditions; and recirculation at a
472

for the reactors with SS or carbon cloth anodes, while current rate of 620 mL min-1 , which could have enhanced the rate of mass

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Cu anode in microbial fuel cells www.soci.org

Figure 2. Power density curves of MFCs with (a) Cu, (b) SS, or (c) carbon cloth anodes, and polarization data with (d) Cu, (e) SS, or (f) carbon cloth anodes,
for MFCs acclimated at 1000
(solid lines) or 10
(dash lines) external resistors

transfer from the electrode. The surface area of the anode per
volume of reactor of the previous study (0.26 m2 m –3 , both sides
of the electrode) was also much lower than that used here (99 m2
m –3 , projected area of both sides of Cu mesh; 69 m2 m –3 , based
on mesh wires), providing more solution per electrode area for
corrosion. Power densities above 17–19 W m-2 are not believed
to be possible using microbial biofilms,20 – 22 but other chemical
reactions including corrosion could easily sustain much higher
power densities.
CONCLUSIONS
These results show that Cu electrodes should not be used in MFCs
as anodes. The current using a Cu anode was only stable at 0.003
mA, generating a maximum power density of only 2 mW m-2 ,
similar to abiotic controls (no microbial inoculation). SS produced
a lower maximum current density than carbon cloth, but this
was expected due to the high specific surface area of the cloth
compared with the metal mesh. The use of highly porous and
non-corrosive electrodes is therefore recommended for MFCs. 473

Figure 3. (a) Current generation (10
resistor) and (b) power density curves for an abiotic reactor with a Cu anode.

J Chem Technol Biotechnol 2014; 89: 471–474

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 www.soci.org
ACKNOWLEDGEMENTS
The authors acknowledge support from the King Abdullah
University of Science and Technology (KAUST) by Award KUS-I1-
003-13. We thank Mike Greenwald for help in Cu2+ measurement
using atomic absorption flame emission spectrophotometry.
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