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A Comparison of Air and Hydrogen Peroxide Oxygenated Microbial Fuel Cell Reactors
A Comparison of Air and Hydrogen Peroxide Oxygenated Microbial Fuel Cell Reactors
241
In this study, a two-compartment continuous flow microbial fuel cell (MFC) reactor was used
to compare the efficiencies of cathode oxygenation by air and by hydrogen peroxide. The MFC
reactor had neither a proton-selective membrane nor an electron transfer mediator. At startup,
the cathodic compartment was continuously aerated and the anodic compartment was fed with
a glucose solution. An increase of electrical power generation from 0.008 to 7.2 mW m-2 of
anode surface with a steady-state potential of 215-225 mV was observed within a period of 12
days. The performance of the air-oxygenated MFC reactor progressively declined over time
because of biofilm proliferation in the cathodic compartment. Oxygenation of the cathodic
compartment using 300 mL d-1 of 0.3% hydrogen peroxide solution resulted in a power density
of up to 22 mW m-2 (68.2 mA m-2) of anode surface at a potential of 340-350 mV. The use
of H2O2 for oxygenation was found to improve the long-term stability of the MFC reactor.
Introduction
Although electricity generation in a microbial fuel cell (MFC)
has been known for decades (1), the need for a chemical
mediator and a proton-selective membrane has greatly limited
the economical feasibility of microbiological production of
electricity. Recent studies on the microbial conversion of organic
matter to electricity have demonstrated a direct electron transfer
by microorganisms attached to the anode implying that microorganisms used the electrode as the terminal electron acceptor.
This finding allowed for the development of a mediatorless MFC
(2-4). Furthermore, electricity production has been demonstrated in a two-compartment mediator- and membraneless MFC
(5, 6) and in a single chamber MFC (7-9). This setup essentially
resembles that of a sequential anaerobic/aerobic wastewater
treatment system, suggesting the possibility to co-generate
electricity during a wastewater treatment process (9, 10).
A mediator- and membraneless microbial fuel cell typically
consists of an anaerobic and an aerobic compartment, containing
an anode and a cathode, respectively. Microbial oxidation of
organic matter occurs in the anodic compartment where
electrochemically active microorganisms attach to the anode
surface, which serves as the sole electron acceptor for anaerobic
respiration (2). Substrate oxidation results in the generation of
both electrons and protons. The mechanism of electron transfer
to the anode can be governed by microbially produced extracellular electron shuttles, by components associated with the
bacterial cell wall, or by both mechanisms (11). Protons migrate
through the liquid phase to the cathodic compartment and
electrons move through the external circuit. Oxygen supplied
to the cathodic compartment results in electron and proton
consumption with the formation of water.
Studies in which pure and mixed cultures were used have
shown that the attachment of a broad range of anaerobic
microorganisms such as Shewanella oneidensis, Geobacter
sulfurreducens, and Rhodoferax ferrireducens to the anode
* To whom correspondence should be addressed. boris.tartakovsky@
cnrc-nrc.gc.ca.
10.1021/bp050225j CCC: $33.50
Published 2006 by the American Chemical Society and American Institute of Chemical Engineers
Published on Web 12/02/2005
242
Figure 1. Experimental setup. The reactor was operated in upflow mode with liquid flow from anodic to cathodic compartment. The insert shows
design of the electrode assembly.
Results
Operation of the MFC reactor was started at an aeration rate
of 4 L air LR-1 min-1 in the cathodic compartment, which
provided a dissolved oxygen concentration of 8-9 mg L-1. At
the same time an oxygen concentration of 0.5-1.0 mg L-1 was
measured in the upper part of the anodic compartment in the
vicinity of the separator pad. No oxygen was detected 1 to 2
cm below the separator. When the electrodes were connected
with a 500 resistance, a potential of 3-5 mV was measured.
Consequently, a value of 4 mV was considered as background
and was subtracted from all subsequent measurements.
After a 3 day lag phase, a near exponential voltage increase
was observed and by day 20, the voltage stabilized between
200 and 210 mV (Figure 2). A current-voltage test was carried
out on day 23 of reactor operation. First, an open-loop potential
was measured, and then the external resistance was changed
stepwise from 1000 to 10 with a period of at least 40 min
between the increments to stabilize electrical current after each
243
Figure 2. Power production during the aeration phase (A, the insert
shows H2O2 injection experiment and arrow indicates the onset of the
polarographic test) and H2O2-feeding phase (B, numbers indicate H2O2
loads in mL d-1).
influent
963b
0
0
0
963
air
anode
cathode
anode
2.2
161.3
104.4
73.9
341.8
6.6
11.9
100.4
35.3
105.9
253.5
6.6
1.9
113.3
106.1
64.6
285.9
8.4
H2O2
cathode
6.3
85.2
24.0
99.7
215.2
6.9
a COD equivalents are 1.16, 1.95, 2.4, and 1.07 for 1 g of glucose,
propionate, butyrate, and acetate, respectively. b Based on 500 mg d-1
glucose feeding rate.
244
aeration
(L Laer-1 min-1)
H2O2 load
(mL d-1)
power density
(mW m-2)
1
2
3
4
5
4
0
4
0
2
0.75
0.75
0.25
0.25
0.5
4.3
18.9
2.0
6.7
3.1
Discussion
Conventional wastewater treatment systems often consist of
sequentially connected anaerobic and aerobic units. Anaerobic
acidogenic and methanogenic microorganisms of the anaerobic
unit convert a part of organic matter to methane and carbon
dioxide and the remaining biodegradable materials are degraded
in the aerobic unit by the aerobic microorganisms. The upflow
two-compartment MFC reactor used in this experiment carried
out the same biodegradation sequence. In addition to COD
removal, close proximity of the anaerobic and aerobic compartments allowed for microbial generation of electricity by
microorganisms attached to the anode surface.
Coulombic efficiency of the MFC reactor was evaluated using
the measurements of glucose and degradation intermediates in
the anodic compartment (Table 1). The average amount of CODs
consumed in the anode compartment daily during the aeration
phase was estimated at 375 mg COD d-1 and the substrate
molecular weight was M ) 76 g. The calculations were carried
out for external resistances of 500 and 11 . The 500 external
resistance was used throughout the experiment, while a resistance of 11 corresponded to a maximal observed current
density of 1 mA in the polarographic test (85 mA m-2, Figure
3A). The calculations yielded Coulombic efficiencies of 1.8%
and 4.5%, respectively.
Calculations of Coulombic efficiency during the H2O2 phase
were based on an average value of 428 mg COD d-1 consumed
daily in the anodic compartment (Table 1). In this case, a
Coulombic efficiency of 2.9% was calculated for an external
resistance of 500 used throughout the experiment and an
efficiency of 6.3% was calculated for a maximal observed
current of 1.6 mA (133 mA m-2, Figure 3B). These values are
similar to 3-12% Coulombic efficiency observed in mixed
culture experiments (12).
Overall, the long-term stability and power generation efficiency of the MFC reactor in this experiment were limited by
such factors as proliferation of aerobic microorganisms in the
cathodic compartment and the presence of suspended anaerobic
microorganisms in the anodic compartment. Notably, oxygen
penetration in aerobic biofilms is limited to 200-500 m (16,
17), implying that the core of a sufficiently thick aerobic biofilm
is oxygen-limited. In the experiment, biofilm formation on the
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Acknowledgment
Friendly discussions with Dr. M Gattrell on process electrochemistry are gratefully acknowledged. This is NRC paper no.
47248.
246
(17) Casey, E.; Glennon, B.; Hamer, G. Oxygen mass transfer
characteristics in a membrane-aerated biofilm reactor. Biotechnol.
Bioeng. 1999, 62, 183-192.
(18) Tartakovsky, B.; Manuel, M.-F.; Guiot, S. R. Trichloroethylene
degradation in a coupled anaerobic/aerobic reactor oxygenated using
hydrogen peroxide. EnViron. Sci. Technol. 2004, 37, 5823-5828.
(19) Moon, H.; Chang, I. S.; Kim, B. H. Continuous electricity
production from artificial wastewater using a mediatorless microbial
fuel cell. Bioresour. Technol. 2005, in press.