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Low-cost fuel-cell based sensor of hydrogen

production in lab scale microbial electrolysis cells
Nuria Montpart a, Mireia Baeza b, Juan Antonio Baeza a,*,
Albert Guisasola a
GENOCOV, Departament d'Enginyeria Qumica, Biol
ogica i Ambiental, Escola d'Enginyeria, Universitat Aut
onoma
de Barcelona, 08193, Cerdanyola del Vall
es, Barcelona, Spain
b
Departament de Qumica, Facultat de Ci
encies, Edifici C-Nord, Universitat Aut
onoma de Barcelona, 08193,
Cerdanyola del Vall
es, Barcelona, Spain
a

article info

abstract

Article history:

A fuel cell sensor was demonstrated as a low cost on-line monitoring tool for hydrogen

Received 17 October 2015

producing microbial electrolysis cells (MECs) at lab scale. Hydrogen produced in the MEC

Received in revised form

was oxidized at the anode of the fuel cell generating electricity that could be easily

29 July 2016

monitored. The total electrical current obtained was proved to correlate with the hydrogen

Accepted 24 September 2016

supplied (r2 0.99) and was equally efficient as other reference analytical methodologies

Available online xxx

based on gas chromatography. Signal was repetitive (2.3% variation coefficient, n 12) and
did not show interferences by the presence of other compounds like methane and carbon

Keywords:

dioxide. The fuel cell was coupled to single and double chamber MECs validating its

Hydrogen

applicability as on-line monitoring portable device for quantifying hydrogen production.

Sensor

The use of the fuel cell as an on-line hydrogen sensor offers an alternative to more complex

Monitoring

methodologies and offers the possibility to implement control systems and optimization

Fuel cell

strategies.

Microbial electrolysis cell (MEC)

2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Introduction
In the current oil dependency situation, hydrogen has raised
interest because of being a renewable clean energy vector
whose combustion has no impact on the greenhouse effect
[1]. Biohydrogen production technologies are an interesting
alternative to the common steam reforming of fossil fuels to
chemically produce hydrogen, especially when using waste
streams as feedstock. Microbial electrolysis cells (MECs)
simultaneously allow the treatment and valorization of
wastewater by producing hydrogen.

MEC operation relies on the presence of a group of microorganisms that have the ability to use an external insoluble
electrode as final electron acceptor (known as exoelectrogens
or anode respiring bacteria, ARB) [2e5]. ARB consume organic
matter available in wastewater under anaerobic conditions,
donating the last electron involved in their metabolic pathway
to the electrode. The supply of some electrical energy to
overcome thermodynamic limits allows the flow of electrons
generated on the anode to the cathode, where the abiotic
hydrogen production takes place. The interest of this process
lies on the facts that (i) energy requirements to drive this
process are much lower than those required for water

* Corresponding author. Fax: 34 935 812 013.

E-mail addresses: nmontpartplanell@gmail.com (N. Montpart), mariadelmar.baeza@uab.cat (M. Baeza), juanantonio.baeza@uab.cat
(J.A. Baeza), albert.guisasola@uab.cat (A. Guisasola).
http://dx.doi.org/10.1016/j.ijhydene.2016.09.169
0360-3199/ 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article in press as: Montpart N, et al., Low-cost fuel-cell based sensor of hydrogen production in lab scale microbial
electrolysis cells, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.09.169

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e8

electrolysis (ii) wastewater depuration and valorization are

accomplished and (iii) higher hydrogen yields than with other
biohydrogen producing technologies can be reached [6].
In MEC lab scale studies, analytical methods to monitor the
system performance in terms of hydrogen production may be
an issue because of practical reasons, such as the cost of the
equipment, the system location or the number of replicate
reactors to monitor. Operational reasons, such as too low
hydrogen production, can also impede its detection. The use
of a gas chromatograph (GC) is a common practice in lab scale
studies when aiming at hydrogen production monitoring,
either by off-line measurements or by coupling the reactor
with an on-line GC [7e9]. Both methodologies also require the
connection of a flow-meter to fully quantify the production
[10,11]. Gas production can also be measured on a GC sparing a
flow-meter with a double analysis strategy as presented by
Ambler and Logan [12]. Other analytical techniques described
in the literature for hydrogen detection comprise the use of
membrane inlet mass spectrometry together with a flowmeter system [13] or specific hydrogen sensors [14]. These
techniques are notably expensive and require regular maintenance. The on-line estimation of biohydrogen production
based on conductivity measurements has also been proposed
by Gueguim Kana et al. [15]. The main advantage of measuring
hydrogen production on-line is the possibility to develop
process control techniques that could improve the system
performance.
As a sensor, a device should present certain characteristics, such as high sensitivity and selectivity, robustness, small
response time, ability to transduce the sensor signal to electrical signal, operation at room temperature and low power
consumption. Current materials for gas sensors are semiconductor metal oxides, where the absorption and desorption
of the gas on its surface produces a change on the material
conductivity that can be correlated with the gas concentration. A small amount of catalytic metal is often added to
improve the selectivity and the sensitivity of the gas sensor.
Other currently used methods to monitor hydrogen in biogas
plants are electrochemical sensors [16e18].
A never reported low-cost strategy for on-line hydrogen
monitoring in MEC is presented in this work. A fuel cell
is examined to work for hydrogen production quantification
and, therefore, its potential to give a fast and stable
response, a long lifetime and easy calibration and operation
are tested. The possibility of monitoring hydrogen production with the system proposed in this work is validated
coupling it to an MEC in single chamber and double chamber
configuration.

Materials and methods

Fuel cell sensor
A single reversible fuel cell provided with a cation exchange
membrane was used in this work (54 mm  54 mm  17 mm,
SKU 632000, Fuel Cell Store, USA). A needle was tightly connected to the anodic chamber inlet port, which allowed the
connection to gas collection bags or to the system headspace
(Fig. 1). Epoxy glue (Araldit, Ceys) was used in joints to

Fig. 1 e Fuel cell sensor with connection modification in

the anodic chamber inlet port.

minimize leakages. The cathodic inlet port was left uncapped

to permit free air diffusion into the cathode.
Gas bags with low hydrogen permeability (Ritter, Cali-5Bond, 100 mL and 500 mL) were used to supply the gas sample to the fuel cell for its calibration. A Teflon rubber septum
permitted the connection with the needle from the fuel cell.
The bags were rinsed three times with nitrogen gas and
emptied with a vacuum pump prior to gas sample introduction. The gas sample was introduced to the gas bag via a gas
tight syringe (Hamilton Samplelock Syringe, 1 mL and 10 mL).
High purity gases (hydrogen, nitrogen, carbon dioxide and
methane, Air Products, Inc.) were used to prepare the gas
samples.

Microbial electrolysis cells

Different MECs were coupled to the fuel cell sensor for validation on a real biohydrogen production system. The single
chamber membrane-less MEC was a 28 mL cylindrical methacrylate vessel provided with a 16 mL glass cylinder at the top
tightly sealed with a PTFE rubber cap that enabled gas
collection and connection to the fuel cell. The anode was a
graphite fiber brush (20 mm diameter  30 mm length; 0.21 m2
specific surface area; made with fibers of diameter 7.2 mm,
type PANEX33 160K, ZOLTEK) with a titanium wire core. The
cathode consisted of graphite fiber cloth (3.8 cm diameter,
7 cm2 total exposed area) coated with platinum (5 mg Pt/cm2,
ElectroChem Inc.). Both electrodes, spaced 2.5 cm apart, were
connected to a power source (HQ Power, PS-23023) applying a
potential of 0.8 V. Current intensity was measured quantifying
the voltage drop across a 12 U external resistance serially
connected to the circuit. The cell was easily converted to a
double chamber MEC by coupling an identical module and
placing an anion exchange membrane (AEM) in between (AMI7001S, Membranes International INC). The membrane was
soaked overnight in a 10% sodium chloride solution. Under
this configuration the distance between electrodes increased
to 7 cm. Hold-up volume per module was 35 mL. MEC run in
fed-batch mode at room temperature with acetate as sole

Please cite this article in press as: Montpart N, et al., Low-cost fuel-cell based sensor of hydrogen production in lab scale microbial
electrolysis cells, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.09.169

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e8

carbon source (0.5e1 g L1 initial concentration). The medium

used contained per liter: 0.2 g NH4Cl, 4 mg FeCl2, 6 mg Na2S,
5 mL of mineral media solution and 172 mL phosphate buffer
solution (PBS). Mineral media solution contained per liter: 1 g
EDTA, 0.164 g CoCl2$6H2O, 0.228 g CaCl2$2H2O, 0.02 g H3BO3,
0.04 g Na2MoO4$2H2O, 0.002 g Na2SeO3, 0.02 g Na2WO4$2H2O,
0.04 g NiCl2$6H2O, 2.32 g MgCl2, 1.18 g MnCl2$4H2O, 0.1 g ZnCl2,
0.02 g CuSO4$5H2O and 0.02 g AlK(SO4)2. The PBS stock solution
contained per liter 70 g Na2HPO4 and 12 g KH2PO4. 2-Bromoethanesulfonate was used as methanogenic activity inhibitor
at a concentration of 50 mM. In the double chamber MEC
configuration, the catholyte was a 100 mM PBS solution. The
cell content was completely replaced with fresh medium
when the batch cycle finished. MEC were sparged with nitrogen for 10 min (50 mL N min1) after feeding to guarantee
anaerobic conditions. The fuel cell was also rinsed with nitrogen before its connection to MEC.

Performance indexes
Voltage response in the fuel cell and MEC was monitored by
means of a 16-bit data acquisition card (Advantech PCI-1716)
connected to a personal computer with a software developed in LabWindows CVI 2013 for data acquisition. Current
intensity (I) in the fuel cell and MEC was calculated measuring
the voltage drop (V) across a resistor (Rext) according to Ohm's
law (Equation (1)).
I V=Rext

(1)

The electrical charge circulated in the system was calculated as presented in Equation (2):
Ztf
Itdt

Chargecoulombs

(2)

ti

Theoretical coulombs supplied to the fuel cell as hydrogen

could be estimated from the volume of hydrogen fed to the
fuel cell as presented in Equation (3):
Charge coulombsH2 nH2 $2$F

(3)

where nH2 is the moles of hydrogen, calculated with the ideal

gas law at the current temperature, 2 are the moles of electrons available per mole of hydrogen and F is Faraday's constant (96,485 C/mol e).
Coulombic recovery for standards was calculated as the
percentage of coulombs measured by the fuel cell (Equation
(2)) with respect to the theoretical coulombs calculated from
hydrogen supplied (Equation (3)).
Gas chromatography (Agilent Technologies, 7820-A) was
used as reference method for hydrogen analysis using a
thermal conductivity detector and argon as carrier gas (oven
temperature 40  C, HP-mole sieve column, detector temperature 220  C). Gas quantification was performed according to
the procedure presented by Ambler and Logan [12], following a
double run methodology. In this methodology, the sample is
analyzed in a first run, then a known volume of nitrogen is
added as a reference compound and the resulting mixture is
again analyzed. Mass balances calculations including the
change in sample composition and the volume added allow

the calculation of the initial gas volume as presented by

Equation (4):
Vtotal;i

Vadded;N2  Vrun 1 $xN2 ;run 1  Vadded;N2 $xN2 ;run 2 Vrun 1 $xN2 ;run 2
xN2 ;run 2  xN2 ;run 1
(4)

where Vtotal i is the initial total gas volume in the bag, Vadded;N2 is
the known volume of nitrogen added, Vrun 1 is the volume
injected in the GC in the first analysis, and x is the molar
fraction of nitrogen in the first analysis or the second as
indicated on the subscript. The output of gas chromatography
analyses is the volumetric fraction (or molar fraction) per
compound, thus, knowing the total initial volume, the initial
volume per compound can be calculated.
Acetate concentration was analyzed from 0.22 mm filtered
samples with gas chromatography using a flame ionization
detector and helium as carrier gas (oven temperature
85e130  C, ramp of 3  C min1, 130e220  C, ramp of
35  C min1, nitroterephthalic acid modified PEG capillary
column, detector temperature 275  C).

Results and discussion

Description of the system
The ability of the fuel cell to work as a sensor was initially
tested. Two fuel cells were used in parallel in the tests performed in this work to account for the device variability,
observing no significant differences. For each test, the fuel cell
was connected to a gas bag containing a known volume of
hydrogen gas. Hydrogen supplied diffused to the anodic
chamber of the fuel cell where it was oxidized. Protons
migrated through the cation exchange membrane whereas
the electrons flowed along the electrical circuit to the cathode
producing a voltage signal. In the cathodic chamber, oxygen
was reduced to water. Voltage reached a maximum in the first
minutes of the test and, then, decreased progressively
(Fig. 2A). Current intensity was calculated with Equation (1)
using the measured voltage and then Equation (2) was used
to calculate the total electrical charge. Fig. 2B shows the current intensity obtained with different external resistances for
an identical hydrogen volume supplied. As can be observed,
the system reached higher current intensity for an external
resistance of 12 U, showing less limitation than the external
resistances of 100 and 350 U.
From a chemical engineering point of view [19], the fuel
cell operation is a reaction driven by a non-porous heterogeneous catalyst and hence there is external mass-transfer
limitation of hydrogen from the bulk gas to the anodic
catalyzer surface, and chemical reaction with its three steps
of reactant (hydrogen) adsorption, surface reaction and
product (protons) desorption. In addition to these classical
heterogenic catalysis steps, the external electrical resistance
of the fuel cell limits the maximum rate of the surface reaction, reducing the electron flow through the electric circuit. Regarding the experiments performed with different
external electrical resistances, the current intensity profiles
obtained with 100 and 350 U were lower than the profile obtained with 12 U. As the only operational change is the

Please cite this article in press as: Montpart N, et al., Low-cost fuel-cell based sensor of hydrogen production in lab scale microbial
electrolysis cells, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.09.169

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40

3.5
Current intensity (mA)

A
Voltage (mV)

30
t vs V-10mL,12ohm

20

10

3.0
2.5
2.0
1.5
1.0
0.5
0.0

10

20

30

40

10

Time (h)

20

30

40

Time (h)

Fig. 2 e (A) Voltage monitored for the fuel cell after supplying 10 mL of hydrogen (external resistance of 12 U). (B) Current
intensity for the fuel cell after supplying 10 mL of hydrogen for external resistance of 12 U (solid), 100 U (dashed) and 350 U
(solid gray).

Selection of external resistance and system calibration

When the fuel cell is conceived to work in series with another
device, for example if it is to be used as a sensor like in this
work, it is crucial that the fuel cell is not the limiting step of
the process. The rate at which the electrochemical reactions
take place in a fuel cell is dependent on the external resistance
that is used to close the electrical circuit. Hence, a set of
external resistances (i.e. 12, 50, 100 and 350 U) were tested to
evaluate which load would offer the maximum quantification
of the volume of hydrogen supplied to the fuel cell (Fig. 3).
Such quantification was determined in terms of percentage of
coulombs recovered, i.e. coulombs measured referred to
hydrogen supplied in units of coulombs.

As shown in Fig. 3, higher external loads resulted in

lower coulombic recoveries, which were also more
dispersed. These observations were most probably caused
by the electrical current limitations mentioned before, since
high external resistances led to slower surface reactions
and, thus, to higher hydrogen retention time in the system
which would have led to an increase in hydrogen leakage to
the exterior. Hydrogen leakage in these systems can become
a significant issue if it is not well addressed. The highest
coulombic recovery was achieved with the 12 U external
resistance, allowing an average recovery of 71%. This value
can be considered high because the usual efficiency reported for fuel cells is around 40e60% of useful output energy versus total input energy [21]. Considering the results
of Fig. 3, the 12 U resistance was used in all the following
tests.

80
Coulombic recovery (%)

increased external resistance, it means that the surface reaction is the slower step in the overall process, at least in the
cases of 100 and 350 U. The exact value of external resistance
where surface reaction becomes limiting depends on the
flow convection around the cathode as well as on the cathode
physical characteristics. In our system, no external mass
transfer limitation seems to exist for the 100 and 350 U resistances except after 10 h of operation, when the change in
the intensity profile indicates some external mass transfer
limitation effect due to very low hydrogen concentration in
the bulk. The observed constant decrease of current intensity
is related to the decrease of hydrogen concentration in the
gas bag (i.e. current intensity seems to be proportional to the
bulk hydrogen concentration). On the other hand, the results
for the external resistance of 12 U show that external mass
transfer seems to be limiting the observed reaction rate. The
shape of the current profile depends on the diffusion of
hydrogen from the bulk gas of the bag through the needle
and the inlet port of the fuel cell to the surface of the catalyzer, where several zones are exposed to different hydrogen
concentration and these zones are changing with the
decrease of bulk hydrogen concentration during the operation of the cell. Other factors such as water accumulation in
the anode that decreases the catalytic surface may be also
modifying the fuel cell response [20].

60

40

20

0
0

100

200

300

400

External resistance (ohm)

Fig. 3 e Hydrogen recovered (in units of coulombs) as a
function of the external resistance in the fuel cell. Error
bars indicate standard deviation, which was calculated
based on triplicate tests.

Please cite this article in press as: Montpart N, et al., Low-cost fuel-cell based sensor of hydrogen production in lab scale microbial
electrolysis cells, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.09.169

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e8

Even though current intensity was dependent on the

external resistance, reaching lower values for higher loads, a
signal response was immediately detected in all the cases.
This device should have a response time at least one order of
magnitude lower than the process that is being monitored
[22]. Thus, a fast response is needed in a measuring device
aiming at fast hydrogen detection, so that a corrective control
action can be quickly applied. However, a slower response of
the measuring instrument can be accepted for a slow biological dynamics as in an MEC.
Once the adequate external resistance was set, the fuel cell
was calibrated to get a correlation between the coulombs
measured in the fuel cell and the actual moles of hydrogen
supplied. The system was considered to be at 1 atm pressure
during these calibration tests. As shown in Fig. 4, a good linear
correlation with high repeatability was obtained for the
quantification. The highest variability was observed for the
highest quantity of hydrogen tested. Higher volumes have
longer analysis time, which favors hydrogen diffusion and
increases the probability of human error when sampling the
gas, increasing the standard deviation of the results.
In terms of hydrogen volume, also a lower detection limit
for the fuel cell was of interest. Indeed, 4 mL of hydrogen was
found to be the lowest volume that permitted its quantification at the highest attainable coulombic recovery, i.e. 71%.
A total of 12 consecutive experiments (containing 10 mL of
hydrogen each) were used to assess the repeatability of the
fuel cell as an electrochemical sensor. The fuel cell quantified
an average of 71.09 C with a variation coefficient of 2.3%.
Values for the variation coefficient lower than 5% are generally describing high repeatability.

concentration. Hence, it has been considered as a reference

method to compare with the one presented in this work.
Standard mixtures of hydrogen and nitrogen were quantified in triplicate by gas chromatography and with the fuel
cell. A strong positive correlation (slope very close to the unity)
was obtained when comparing both methods, indicating that
these methodologies were analogous regarding hydrogen
quantification (Fig. 5). The least-square linear regression test
fitting the five averaged points was used to make the statistical evaluation of the fuel cell sensor and the errors associated to slope and intercept. No significant difference was
observed at 95% confidence level (dashed line in Fig. 5). The
slope and intercept were 0.98 0.05 and 0.00 0.03, respectively (r2 0.996; n 5; 95% confidence level).

Evaluation of possible interferences from other biogas

compounds
Methane and carbon dioxide were tested independently in the
device to check that they were not interfering and therefore
no electrical signal was being detected. Neither methane nor
carbon dioxide showed current generation in the fuel cell,
indicating that they did not react and no interference existed.
Another verification test with hydrogen was performed afterward to confirm that no catalytic damages were caused by
these compounds. In both cases, the signal was totally
matching the signal before the tests with carbon dioxide or
methane, and therefore no catalytic loss was experienced in
the system. Methane and carbon dioxide are therefore regarded to be inert in the fuel cell.
Carbon dioxide was proven to be inert when fed independently in the fuel cell. Moreover, mixtures of carbon dioxide

As already mentioned, gas chromatography is the most

common analytical method to measure hydrogen

Charge measured (C)

700
600
500
400
300
200

y = (143 4) x
r2 = 0.99

100

Volumetric gas composition measured

with hydrogen fuel cell

Validation of the fuel cell sensor

1.0
0.8
0.6
0.4
0.2
0.0
0.0

0.2

0.4

0.6

0.8

1.0

Volumetric gas composition measured

with gas chromatography

0
0

Hydrogen supplied (mmols)

Fig. 4 e Fuel cell sensor calibration for coulombs measured
vs. moles of hydrogen supplied. Error bars indicate
standard deviation, which was calculated based on
triplicate tests.

Fig. 5 e Validation of a fuel cell as hydrogen monitoring

device with a reference method (gas chromatography, GC).
The linear regression equation obtained was
y 0.98(0.05) x 0.00(0.03), r2 0.996. Average values
from triplicate tests for GC and fuel cell (symbols) and their
corresponding standard deviation, linear regression (solid
line) and 95% confidence intervals (dashed line).

Please cite this article in press as: Montpart N, et al., Low-cost fuel-cell based sensor of hydrogen production in lab scale microbial
electrolysis cells, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.09.169

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e8

with hydrogen were also tested to investigate about the

possible poisoning effects of carbon monoxide, which can be
produced by the reverse water gas shift reaction. Carbon
monoxide is reported to adsorb on the catalyst, decreasing the
efficiency of the fuel cell [23e25]. Nevertheless, no catalytic
loss was observed in the system studied along all the operational period of this study.
Regarding the lifetime of the device, the system was tested
for a period of four months without seeing any loss in its
measuring capacity. A periodical control analysis and, if
necessary, a calibration of the device would be recommended.
An option to avoid catalytic loss by carbon monoxide formation includes the possibility of trapping carbon dioxide in a
sodium hydroxide solution before the gas mixture arrives to
the fuel cell.

Implementation in a hydrogen-producing microbial

electrolysis cell
A last test using the fuel cell as an on-line monitoring tool was
performed connecting it in series with an MEC, both in single
chamber (Fig. 6A) and double chamber configuration (Fig. 6B).
Fig. 6C and D show, respectively for each configuration, the

current intensity monitored for the MEC and the fuel cell. Both
signals followed a similar trend although the response for the
fuel cell was lower than for the MEC. Lower current intensities
in the double chamber configuration were result of a lower
applied voltage and higher spacing between electrodes.
The cumulative moles of hydrogen produced (Fig. 6E and F)
were quantified (i) according to the fuel cell response by
applying Equation (2) with the intensity measured in the fuel
cell and using the calibration shown in Fig. 4, and (ii) according
to the MEC response by applying also Equation (2) but with the
intensity measured in the MEC and using Equation (3),
assuming that the charge calculated with Equation (2) was
devoted to hydrogen production. As can be observed in Fig. 6E,
the theoretical production of hydrogen according to the MEC
response for the single chamber MEC configuration was
higher than the maximum attainable moles according to the
substrate fed. This observation and the coulombic efficiency
higher than 100% were indicators of a case of hydrogen recycling in single-chamber MEC. In such situation, hydrogen
electrochemically produced in the MEC is used as electron
donor by homoacetogenic bacteria producing acetate [26,27],
which contributes to additional current generation in the
system. Another consequence of hydrogen recycling is that

Fig. 6 e Implementation of the fuel cell as an on-line hydrogen production monitoring tool in a single chamber MEC (left) and
in a double camber MEC (right). A, B: Experimental setup. C, D: MEC current intensity signal (solid) and fuel cell response
(bold). E, F: Hydrogen production measured by the fuel cell (bold), estimated according to the MEC current intensity (solid),
and the maximum attainable according to substrate fed (dashed).
Please cite this article in press as: Montpart N, et al., Low-cost fuel-cell based sensor of hydrogen production in lab scale microbial
electrolysis cells, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.09.169

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e8

hydrogen measured is lower than expected based on the MEC

signal. Actually, hydrogen measured by the fuel cell only
accounted for 44% of the theoretical production based on MEC
current intensity and 55% of the maximum attainable
hydrogen production based on the acetate provided. However,
these values lower than 100% are not indicating an incorrect
quantification of the hydrogen produced by the fuel cell.
Conversely, this quantification is more accurate than both
methodologies. The quantification based on MEC current intensity has the problem created by the recycling phenomena,
while the theoretical value based on the amount of acetate
added does not consider any other biological process that
could occur as biomass growth, methanogenesis or hydrogen
recycling.
On the other hand, the monitored signal matched perfectly
the hydrogen production in a double chamber MEC configuration (i.e. in absence of any hydrogen recycling phenomena).
Fig. 6D and F show a perfect description of hydrogen production with a 100% quantification of the theoretical hydrogen
production. The overlapping of hydrogen production estimation by the fuel cell and by the MEC indicates a perfect operation of the double chamber MEC, where all the acetate
consumed generates electrical current that is used by the
cathode to generate hydrogen. Double chamber MECs are
better for producing hydrogen, avoiding the problems of microbial competence for substrate as in single chamber cells
(especially homoacetogenesis and methanogenesis). However, double chamber MECs have also other problems as
increased pH gradient between cathode and anode, which
decreases greatly the hydrogen production performance [28].

Practical implications
The use of a fuel cell at lab scale to monitor hydrogen production is proposed and evaluated as an alternative to more
complex analytical methods, such as gas chromatography.
There are advantages and drawbacks for both systems, but in
the end the possibility of using one or another is highly
dependent on the system to be monitored (configuration, use,
location, budget, etc.).
Regarding gas chromatography, the advantages of the
system include the possibility to detect more than one gas
compound, not only hydrogen, and the availability of commercial on-line GC. Nevertheless, the device is notably
expensive (thousands of euros) and it requires the consumption of utility gases. Also, when it comes to the analysis per se,
a double analysis is required in order to be able to quantify the
volume produced (as in Ambler and Logan [12]). Alternatively
the system can be connected to a flow meter to measure total
gas production, increasing the costs.
On the other hand, the fuel cell as a device to monitor the
hydrogen produced represents a completely affordable instrument (less than 50 V in this case), which can easily be set
on-line with the system to monitor and that only needs a
conventional data acquisition system to record voltage. Being
selective for hydrogen, it can be a perfect option in systems
where pure hydrogen is produced, such as double chamber
MECs. In a single chamber MEC configuration, or in other
anaerobic systems, only hydrogen produced or its relative
composition can be measured.

The time required to perform the analysis can be quite long

when using it off-line, in the range of few hours, since
hydrogen arrives to the reacting catalytic surface only by
diffusion, which can be slow due to the reduced driving force
when the hydrogen concentration decreases. This possible
problem could be minimized by using a fuel cell with higher
capacity.
The fact that the fuel cell will consume the product of interest is not an important drawback at lab scale. More
importantly, having a device able to monitor on-line with high
reliability the hydrogen produced also allows the implementation of control strategies, which can end up improving
the whole performance of the system.

Conclusions
A low cost fuel cell is presented in this work as an alternative,
transportable and robust methodology to quantify hydrogen
production in MEC at lab scale. Tests revealed the high
repeatability of the system, showing a high correlation of the
signal with the amount of hydrogen supplied. A strong correlation was also obtained when comparing the methodology
presented here with gas chromatography as a reference
method and no significant differences were observed at 95%
confidence level. In addition, neither interference due to other
biogas compounds nor loss of catalytic activity during all the
operational period were observed. The use of the fuel cell as
on-line monitoring device measuring biohydrogen production
in MEC at lab scale was also demonstrated in single and
double chamber configurations.

Acknowledgements
N. Montpart acknowledges the support of Universitat

noma de Barcelona with a PIF pre-doctoral grant. N.
Auto
Montpart, J.A. Baeza and Albert Guisasola are members of the
GENOCOV group (Grup de Recerca Consolidat de la Generalitat
de Catalunya, 2014 SGR 1255).

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Please cite this article in press as: Montpart N, et al., Low-cost fuel-cell based sensor of hydrogen production in lab scale microbial
electrolysis cells, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.09.169