Chemical Engineering Journal 324 (2017) 228–236

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Chemical Engineering Journal

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

Cathode deposits favor methane generation in microbial electrolysis cell

Marc Sugnaux a, Manuel Happe a, Christian Pierre Cachelin b, Andrea Gasperini a, Maxime Blatter a,
Fabian Fischer a,⇑
a
Institute of Life Technologies, HES-SO Valais, University of Applied Sciences Western Switzerland, Route du Rawyl 64, CH-1950 Sion, Switzerland
b
Systems Engineering, HES-SO Valais, University of Applied Sciences Western Switzerland, Route du Rawyl 47, CH-1950 Sion, Switzerland

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Hydrogen free methanisation was

possible with cathode deposited with
Ca, Fe and P.

Highly pure methane was in-situ
extractable with polyethersulfone
membrane.

Activated sludge inhibited hydrogen
evolution despite favorable
conditions.

Low energy consumption in room
temperature bioelectric
methanisation.

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

Article history: Cathodes in microbial electrolysis cells are exposed to poisoning in particular when using activated
Received 17 March 2017 sludge as substrate. In this work, it was examined how well hydrogen generation is possible and what
Received in revised form 2 May 2017 kind of membrane protection is sufficient to produce hydrogen from activated sludge. Also model micro-
Accepted 3 May 2017
bial electrolysis was performed to simulate hydrogen evolution in a mimic biological environment at
Available online 6 May 2017
pH = 7. With activated sludge, it was found that electrodeposition of calcium, iron and phosphor and
other impurities inhibited the hydrogen evolution reaction. Applying 2.0 V, the biogas productivity
Keywords:
increased notably as if it induced rather chemical hydrolysis than hydrogenation and favored methanisa-
Microbial electrolysis cell
Deposits
tion. This MEC generated methane in up to highest purity, 67–97%. In addition, this room-temperature
Inhibition methanisation consumed far less energy than with comparable mesophile conditions.
Hydrogen Ó 2017 Elsevier B.V. All rights reserved.
Methane
Activated sludge

1. Introduction
Electricity or microbial electrolysis cell (MEC) supported green
methanisation bears a great industrialization potential [1]. The
base for this technology is that the MEC generates hydrogen at a
low applied voltage of 0.135 V at pH = 7 [2–4]. The overpotential
in the MEC is about ten times smaller than with the HER using
water, where an applied voltage of 1.23 V is needed [5]. But what
happens when the electrode becomes polluted by components that
⇑ Corresponding author.
E-mail address: fabian.fischer@hevs.ch (F. Fischer).
are deposited on the cathode’s catalytic surface? This deposit prob-
lem contrasts to chemical water electrolysis where rapid poisoning
is avoidable [6]. Nevertheless, MEC supported hydrogen generation
research is pursued as water electrolysis is costly [7]. The MEC is
thought to be a competitive alternative and could even outperform
fossil fuel based hydrogen generation.
In microbial electrolysis not only the microbes and the pH but
also the substrate quality defines the performance. The ideal sub-
strates comprise acetate [8], glycerol [9], sugar beet juice [10]
waste water, and also the less easy to digest activated sludge
[11]. From all feed stocks, waste water is the least expensive and
most abundant but also most polluted. Single cell microbial elec-

http://dx.doi.org/10.1016/j.cej.2017.05.028
1385-8947/Ó 2017 Elsevier B.V. All rights reserved.
 M. Sugnaux et al. / Chemical Engineering Journal 324 (2017) 228–236 229

trolysis is turned less effective by poisoned cathodes, but also by provide beneficial or detrimental effects on hydrogen and methane
the presence of methanogens that metabolize hydrogen. To tackle generation. The results were compared to model reactions realized
these problems a number of methods eventually prevent methane in a voltammetry setup to discuss, if there are new mechanisms
formation during microbial electrolysis. The most consequential using microbial electrolysis cell to digest activated sludge.
method is to separate anode and cathode using a dual chambered
microbial electrolysis cell. In this two half-cell’s architecture, H2
evolves only from the compartment hosting the cathode whereas 2. Materials and methods
methane is retained in the anodic half-cell [12]. Conversely, with
the single cell MEC design hydrogen is freely available to be metab- 2.1. Microbial electrolysis cell construction
olized into methane.
But why methane is generated in MECs? It is because the anaer- A MEC-Stack was designed with Inventor CAD software and
obe MEC is an ideal habitat for methanogens [13]. They originate build in-house. Based on this a 33 L tank with 9 cathode and 10
from all kind of living systems, which depend on anaerobic diges- anode cassettes was constructed using PVC-U (Angst Pfister,
tion to gain energy and nutrients. A prominent example for this Switzerland) [33]. The modular stack architecture allowed elec-
process is the well-known gastric grass digestion in the cow stom- trode exchange and variable positioning in the principal tank
ach [14]. These microbes gain energy from the biological Sabatier chamber (492  280  298 mm) (Fig. 2). The anodes were made
process, which is by thermochemical analysis exothermic (Eq. from reticulated vitreous carbon (RVC), 3% density and 100 ppi
(1)) [15]. The natural methanogenic fusion of carbondioxide and (ERG aerospace, USA) 200  18  130 mm representing 2.9 m2 of
hydrogen into methane reduces the amount of extractable hydro- true surface per anode. The cathodes were from nickel steel (BIBUS
gen from the MEC [16]. METALS AG, Switzerland) 190x130x2 mm. Alternatively platinum
In order to prevent methane generation, methanogen-selective sputtered carbon felt with an equal geometrical surface was
antibiotics were found as effective methanogenesis inhibitors, but
bacteriostatic survival enabled methanogens to recover [17]. Also
chemical inhibitors, such as 2-bromoethanesulfonate or lumazine,
were examined to suppress methanogens [18]. Exposing the culti-
vation to UV light also stopped methanisation [19]. Another
method is to vent the MEC with air-oxygen because O2 is toxic to
methanogens as they are strictly anaerobe [2]. Temperature reduc-
tion is another practical approach to limit methanogenic activity
and favors hydrogen production. This is a possibility for waste
water treatment plants in moderate climate zones where waste
water is often cold [20]. Lowering the pH is another means to
reduce methanogen activity although pH regulation with a chem-
ical base drives up process cost [21].
Another solution is not to inhibit methanogens but to exploit
this bioelectrocatalytic methanisation process as it works at ambi-
ent temperature what saves energy, and what contrasts to com-
monly used mesophile conditions at 37 °C [22]. There is also the
hope that methanogen species will even accept CO2 and H2 from
external sources to generate methane. Here in particular Methan-
othermobacter marburgensis [23] and M. thermautotrophicus [24]
are discussed for such use.
CO2 þ 4H2 ! CH4 þ 2H2 O DH ¼ 165kJ=mol ð1Þ
In addition, methane is easy to handle and can be distributed
through existing gas pipelines. Therefore the most interesting fea-
ture to study MEC based methanisation is its presumed capacity to
increase the overall biogas exhaust and enrich the methane frac-
tion obtained from methanisators [25]. In addition, the biogas
purification cost will drop as less CO2 is contained in the biogas
exhaust [26,27].
There is also the hope, and some experimental evidence, that a
direct electron transfer from the cathode into methanogens [28] is
possible, it could facilitate the metabolic carbon reduction catalysis
[29,30]. This faculty was in particular observed with Methanobac-
terium palustre where a low applied voltage produced methane in
high coulombic efficiencies [29,31]. With certain microbes also
carbon-carbon bond formation is possible using CO2 as substrate
in direct electron transfer mechanism with equally high coulombic
efficiency [32]. The next step is to feed CO2 from outside sources
into the MEC used as a biocatalytic entity. In this case biofuel pro-
duction is decoupled form biomass feed. Fig. 1. Single and dual chambered MECs for either pure hydrogen or pure methane
In this work bioelectric microbial hydrogen generation and generation using activated sludge. A) Dual chambered microbial electrolysis cell
with exoelectrogenic microbial (E) biofilm and cathode producing hydrogen gas. B)
methanogenesis was performed in a 33 L stacked microbial elec- Single chamber MECs produces methane based on exo-electrogenic microbes (E)
trolysis cell operated in batch mode using activated sludge at room which release protons and electrons on the anode and methanogens (M) which
temperature (Fig. 1). It was examined if deposits on the cathode combine these electrons and protons with metabolic carbon on the cathode.
230 M. Sugnaux et al. / Chemical Engineering Journal 324 (2017) 228–236

Fig. 2. 33-L microbial electrolysis cell (MEC) with 10 anodes (A) and 9 cathodes (C). Top left: a fully assembled MEC stack. Bottom left: top view on electrodes stack, grey
cassettes represent anodes (A), dark cassettes cathodes (C). Top right: single cathode cassette from PVC with cathode and gas exhaust. Bottom right: single reticulated
vitreous carbon anode in PVC holder.

employed. The cathodes were fixed in PCV frames, which allowed
to affix NafionÒ N117 proton exchange membranes (PEM) (Ion
Power, Germany) or Polyethersulfone membranes 0.2 lm on both
sides of the cathode. With the Nafion PEM the cathode cassettes
became half cells (CNaf) for dual chambered MEC processing
(Fig. 3c). On top of the cathode chamber a gas exhaust chimney
was connected to gas collection tubes. Two gas tight plastic cable
glands (RS Components GmbH, Switzerland) were integrated in
the outer reactor wall for gas harvesting tubes and electric cables.
A milligas counter MGC-1 V3.2 (Ritter, Germany) allowed gas
quantification and a gas sampling port to take samples with a syr-
inge for composition analysis.
Abbreviations used to describe variable MEC-Stack configura-
tions: A = anode; C = cathode; CNaf = cathode cassette with Nafion
membrane, CPES = cathode cassette with polyethersulfone mem-
brane. As an example for the abbreviation use, the largest possible
membrane free single MEC was a stack named like this: [ACACA-
CACACACACACACA] or written in condensed form as [A(CA9]
(Fig. 2).
2.2. Dual and multi chamber MEC batch operation
Cathode cassettes with membranes allowed dual and multi
chambered MEC batch operation (also continuous mode was possi-
ble but not realized). The electrodes therein were from carbon felt,

Fig. 3. Electrode cassettes: a) Anode (A) with reticulated vitreous carbon. b) Nickel cathode (C) in PVC frame without membrane. c) Cathode cassette with polyethersulfone
membrane (CPES) representing a confined space used as half-cell. Or with a Nafion membrane, representing a CNaf type cathode cassette (no picture, identical to (c).
 M. Sugnaux et al. / Chemical Engineering Journal 324 (2017) 228–236
sputtered with platinum at 0.02 mbar, 60 mA for 160 s on both
sides (total surface 500 cm2) and affixed behind Nafion N117 mem-
branes (Fig. 3c). Then the cathode cassettes (half cells) were
inserted into the MEC tank in between RVC electrodes and filled
with 0.01 M phosphate buffer of pH 7. Depending on experimental
needs one or more cathode cassettes were added to the stack con-
taining in general all 10 RVC anodes to ensure the same quantity of
electrons and protons are produced to uncover if the cathode sys-
tem is the limiting factor in hydrogen evolution. In realized exper-
iments the following four setups were used (i-iv): (i) A single
cathode (CNaf) was inserted in the center of the stack [A5CNafA5].
(ii) A second cathode (CNaf) in alternation with a RVC anode close
to the central cathode [A4(ACNaf)2A4] (iii) and so for the third [A4-
(ACNaf)3A3] and the forth (iv) [A3(ACNaf)4A3]. Finally, activated sew-
age sludge was added to the remaining anode space (up to 17 L).
The activated sludge was obtained from a waste water treatment
plant (WWTP) (Châteauneuf, Switzerland). This activated sludge
was taken just before fed to the methanisation unit of the plant
with an average COD of 12 gO2/L (COD strength depended on the
WWTP’s operation state). Initially, the MEC-Stack was acclimatized
with activated sludge for up to three weeks until a stable open cir-
cuit potential (OCP) was established and then emptied, but bio-
films were not removed. Then again filled with new activated
sludge and once the OCP turned stable, hydrogen production was
started by applying a voltage with a power supply. After this star-
tup time it was thought that eventually remaining oxygen was
reduced to water. The experiments in this work were all conducted
as batch processes. The stacks in all experiments were intercon-
nected by parallel wiring in order to have the same overpotential
in the whole reactor. In some experiments, to enhance hydrogen
content, 30 g of sodium acetate was added to the activated sludge.
Also pseudo dual chambered microbial electrolysis cell use with a
polyethersulfone membrane instead of Nafion was realized accord-
ingly. In this latter setup the catholyte consisted of the cultivation
medium fraction that filtered (that migrated) through the PES
membrane into the cathode.
2.3. Single chamber MEC batch processing
The single cell 33L-MEC contained 10 anodes (A) and 9 cathodes
(C) without membranes. The electrodes were placed in alternation
[A(CA)9] (Fig. 2) and prepared for batch processing. The cathodes
were from nickel steel (BIBUS METALS AG, Switzerland) and the
anodes from RVC (ERG aerospace, USA). Activated sludge (as
described before) was added and methane (in general no H2 was
produced) evolution started. Initially, no applied voltage was used
in order to control if an active biofilm was present. Then new acti-
vated sludge was added and processed under an applied voltage
and this at room temperature (22 °C). Chemical oxygen demand
(COD) use was assessed in the beginning and the end of the pro-
cess. The evolving biogas was analyzed for composition by micro
gas chromatography.
2.4. Gas analysis
Gas samples were analyzed with a micro-GC 490 (Agilent, USA)
using a MS5A column for (H2, O2, N2 and CH4) and a PPU column
(for CO2 and CH4). A micro-thermal conductivity detector (mTCD)
(Agilent, USA) was added. The columns were operated at 80 °C.
The pressure in the first column was set to 200 kPa and in the sec-
ond to 150 kPa.
2.5. Acetate dosage by HPLC
Acetate concentration in activated sludge was determined by
HPLC using an Agilent 1100 Series apparatus with an Aminex
231
HPX-87H column heated to 35 °C connected to a RID detector.
10 ml Samples were taken from the methanisation mixture and
centrifuged at 10,000g for 10 min in a MR20-R centrifuge (Awel,
France). The supernatant liquid was filtered through 0.45 mm PTFE
filter EXAPURE (Alys-Technologies SA, Switzerland) before injec-
tion to the HPLC and eluted with 5 mM sulfuric acid at a rate of
600 ml/min under 90 bars.
2.6. Chemical oxygen demand
Chemical oxygen demand (COD) was used as a parameter which
showed the real and possible conversion of organic mass contained
in activated sludge. The COD assessment goes beyond what
microbes usually can convert, but as an outside applied voltage
was used a higher carbon conversion (deeper oxidation) was not
excluded and the COD was therefore considered an adequate mea-
sure to use.
The COD was determined by the potassium dichromate method
[34]. Three solutions were prepared: Solution 1: 0.04 mol/l
K2Cr2O7, 80.0 g/l HgSO4 and 1.80 mol/l H2SO4; Solution 2: 10.0 g/l
Ag2SO4 and 17.4 mol/l H2SO4; Solution 3: 47.0 g/l (NH4)2Fe(SO4)2
6H2O and 0.360 mol/l H2SO4. 5 ml of Solution 1, 15 ml of Solution
2 and 10 ml of sample were added to a 300 ml single necked flask
with reflux condenser. The mixture was heated for two hours at
reflux, let cool to room temperature and 50 ml demineralized
water (milliQ) was added to reach a total volume of 80 ml. Potas-
sium dichromate in excess was titrated with Solution 3 using fer-
roïne as indicator. The COD was calculated from the equation:
COD = 8000.C.(V1  V2)/V0; C = concentration of the titration Solu-
tion 3 [mol/l]; V1 = Volume Solution 3 for the blank titration
[ml]; V2 = Volume of titration Solution 3 for the sample [ml]; V0 -
= Volume of the sample [ml].
2.7. Electrokinetic parameters of the hydrogen evolution reaction at
neutral pH
Exchange currents (jo) and activation energy (Ea) determina-
tions at pH 7 with the hydrogen evolution reaction (HER) were per-
formed using cyclic voltammetry for nickel (slice 8 cm2) and
platinum (foil 2.1 cm2) as control. The electrodes were cleaned in
an ultrasonic bath with acetone. Cyclic voltammetry measure-
ments were carried out with a three-electrode cell using a mercury
sulfate electrode MSE (E° = +0.64 V vs SHE) as reference electrode
and a platinum wire as counter electrode. Initially a polarisation
sweep was performed with both electrodes at pH 7 at a scan rate
of 50 mV/s using a 1 M NaClO4 to find the potential window for
the HER under given conditions. Then a Tafel plot (current density
versus overpotential) was recorded at 1 mV/s rate. The tempera-
ture dependence for activation energy (Ea) determination was
scanned at 5 mV/s between 20 °C and 40 °C obtaining an Arrhenius
plot (lnk versus 1/T). As electrolytes a solution 1 M of NaClO4 and
optimized to pH = 7 with NaOH 0.01 M (a K2HPO4 buffer 0.5 M
optimized to pH = 7 with H2SO4, (a solution 0.5 M of Na2SO4 and
NaOH 0.01 M). The proton concentration was thought to be con-
stant using this electrolyte and to encounter no proton transfer
limitations maintaining a pH = 7. This electrolyte was renewed
after each experiment.
2.8. ICP-OES for the analysis of deposits on cathodes
The electrodeposited layer on the cathode surface was
scratched from three different electrodes. 5 mg of each sample
were then dissolved in 10 ml of a 2% HNO3 solution (Fluka analyt-
ical, Switzerland) and analyzed with an ICP-OES Varian 720-ES
(Varian Inc., USA). An elemental scan calibrated with internal stan-
232 M. Sugnaux et al. / Chemical Engineering Journal 324 (2017) 228–236
dards was performed on each sample and the averaged ratio for
detected elements was calculated.
3. Results and discussion
The scale-up microbial fuel cell (MEC) stack reactor provided a
total volume of 33 L and was designed for continuous and batch
processing. However, it became quickly apparent that processes
on this scale using in particular activated sludge needed batch con-
ditions to generate comparable data. Therefore all experiments
were performed in batch mode. The principal reason was that acti-
vated sludge was not producing large quantities of hydrogen, in
fact it was rather difficult to generate any hydrogen. Activated
sludge is a predigested substrate and therefore the bioelectricity
supported deeper oxidation under anaerobic conditions in the
MEC is one of the important aspects discussed in the following.
3.1. Introduction to MEC batch processing with and without cathode
deposits
Cathode deposits were found to have favorable properties in
MEC based methanisation. In cases where the cathode was pro-
tected from deposits the electrolysis produced hydrogen, which
was then isolated or converted into methane. This conversion
was mediated by methanogens that were naturally contained in
used activated sludge, and followed a metabolic catalysis mecha-
nism here called Mechanism I (Fig. 4). The more difficult to eluci-
date mechanism occurred under the condition where absolutely
no hydrogen was detectable. Here a quasi-direct bioelectrosyn-
thetic methane production was postulated to occur, Mechanism II
(Fig. 4). The visible cause was that activated sludge promoted the
deposition of materials on the unprotected cathode surface. These
deposits inhibited obviously the hydrogen evolution reaction.
When applying an excessive voltage (2 V), still no hydrogen was
detectable in the head space of the reactor (Table 1, Entries 8–
11). But this higher powered microbial electrolysis enhanced the
conversions of activated sludge into biogas visibly by an important
COD use (Table 2). It was postulated that an increased substrate
hydrolysis became possible, which was beneficial in the methani-
sation. But no mechanistic analysis was possible as pH measure-
Fig. 4. Conversion of biogas-CO2 into methane in a MEC based on an applied voltage. Mechanism 1: in-situ produced hydrogen is converted with CO2 into methane mediated
by methanogens. Mechanism II: Electrons from the anodic waste oxidation are directly or by mediators transferred into the microbe to reduce CO2 and no intermediate
hydrogen evolution takes place. These mechanisms were expected as long as the pH remained neutral as needed in biological environments.
ments on electrode surfaces were impossible, what is known as
an unresolved problem. In any case with activated sludge the cath-
odes became encrusted with solid deposits (Fig. 5). In particular
iron, calcium and phosphor were deposited on the nickel cathodes
according to ICP-OES analysis. Iron originated from influent waste
water and the supplemental addition of FeCl3 to remove phosphate
during waste water treatment. Calcium is naturally contained in
waste water. Also other elements were deposited, but in minor
quantities. The deposits very likely reduced the catalytic activity
for the HER and eventually favored instead a direct or mediated
electron reduction reaction of CO2, Mechanism II (Fig. 4). As the
Mechanism II cannot be directly observed, this is discussed in a
later section based on the performance of a series of model
experiments.
3.2. Cathode deposits favored methanisation
Methane generation in the scale-up MEC was well possible with
polluted cathodes. These cathode deposits suppressed the hydro-
gen formation what is in favor of the safety of future methanisation
installations in urban areas. To investigate these unprecedented
observations a 33L-MEC single cell tank reactor with 19 electrodes
[A(CA)9] was used (Fig. 2). The nickel plate cathodes were in direct
contact with activated sludge. The methane fraction increased with
rising applied voltage (Table 1, Entries 8–11) in a series of batch
processes form 55.9% under zero voltage to 62.5% using 1.5 V,
and increased further up to 68.9% with 2.0 V, all at room tempera-
ture. With 2.0 V also significant higher biogas quantities evolved
than with <1.5 V (Fig. 6). But surprisingly, also with 2.0 V no hydro-
gen gas was detected in the head space of the reactor. The methane
fraction increased with applying higher voltages and the question
was if there was also bioelectrosynthetic methane generation as
no hydrogen gas was detectable in the reactors headspace. The
other assumption was that the hydrolysis accelerated the methani-
sation and methanogens produced more biogas because more sim-
ple predigested substrates became available. In such a scenario the
anode released more protons than under microbial electrolysis cell
conditions and this at a high enough concentration. The cathode
reaction in contrast produced presumably a chemical base but no
hydrogen was visible. The absence of hydrogen was not conform
 M. Sugnaux et al. / Chemical Engineering Journal 324 (2017) 228–236 233

Table 1
Biogas composition depending on operation parameters. All methanisation experiments were performed at room temperature (22 °C). a)Activated sludge was employed as
obtained from the WWTP and in some experiments enriched with 30 g acetate. b)Stacks were composed of A = anodes (RVC), C = cathodes (of Ni) without membrane. Or
membranes such as: CNaf = Nafion PEM protected Pt/carbon fiber cathodes, and CPES = Polyethersulfone membrane protected Pt/carbon fiber cathodes. In general all 10 RVC-
anodes were used and only the cathode number was varied.

Entry Substratea) Stack Typeb) Voltage [V] Anode/Cathode sampling location H2 [%] CH4 [%] CO2 [%]
1 activated sludge/acetate [A5(CPES)A5] 1.5 RVC/Pt/C Cathode 0.41 96.6 3.0
2 activated sludge/acetate [A4(CNaf)2A4] 1.0 RVC/Pt/C Combined 0.002 83.6 16.4
3 activated sludge/acetate [A4(CNaf)2A4] 1.25 RVC/Pt/C Combined 0.0 83.0 17.0
4 activated sludge/acetate [A5(CPES)A5] 1.5 RVC/Pt/C Anode 0.004 81.3 18.6
5 activated sludge/acetate [A4(CNaf)2A4] 1.5 RVC/Pt/C Combined 0.08 80.9 19.0
6 activated sludge/acetate [A5(CNaf)A5] 1.5 RVC/Pt/C Anode 0.045 80.8 19.2
7 activated sludge/acetate [A5(CNaf)A5] 1.5 RVC/Pt/C Cathode 24.5 73.0 2.4
8 activated sludge [A(CA)5] 2.0 RVC/Ni Combined 0 68.7 31.3
9 activated sludge [A(CA)5] 1.5 RVC/Ni Combined 0 62.5 37.5
10 activated sludge [A(CA)5] 0.75 RVC/Ni Combined 0 59.3 40.7
11 activated sludge [A(CA)5] 0.0 RVC/Ni Combined 0 55.9 44.1

Table 2
COD use of processed activated sludge versus applied voltage. The results are from the
A)
scale-up MEC that contained all possible electrodes in the stack [A(CA)9] in single cell
mode. With applying 2.0 V the electrochemical digestion increased considerably as if
there was a hydrolysis pretreatment step of oligomeric and polymeric organic
substrates contained in activated sludge.

Entry U applied [V] D COD [gO2/l] D COD [%]

1 0.0 1.2 10.2
2 0.75 1.6 9.7
3 1.5 3.4 20.2
4 2.0 4.6 82.6

B)

Fig. 5. ICP-OES based elemental analysis of three nickel cathode surfaces after
70 days exposed to activated sludge during methanisation. Nickel originated from
the Ni-cathode, iron originated from FeCl3 addition to remove phosphate, and Ca2+
is naturally contained in any waste water. The other elements were detected in
lower concentrations.

with the hypothesis that a base was formed. But if such a base was
formed equally hydrolyses of non-digestible organic substrates
occurred.
With rising applied voltage also the COD use improved consid-
erably from low 10.2% to 82.6% (Table 2) and correlated with the
equally enhanced biogas productivity. The improved COD use
impressed. That the COD was low upfront was related to the fact
that the process was performed at room temperature. At this tem-
perature any activated sludge methanisation is slow. But once the
process became electro stimulated, it was much faster for reasons
that remain to be discussed. A closer view on the mechanism elu-
cidation is found in Section 3.5. The room temperature process was
energetically more effective as in contrast to mesophilic conditions
no heating of the activated sludge mixture to 37 °C or above was
Fig. 6. Methane productivity at 2.0 V of applied voltage on activated sludge with
RVC anodes and membrane free nickel cathodes. Here all electrodes [A(CA)9] of the
33 L-MEC (Fig. 2) were in use. A) Methane (blue, r) and CO2 (red, j) composition
over time. B) Biogas (red line with quadrants, j) evolution and current (blue line
without markers) at constant voltage.
required. Heating is usually mandatory to reach mesophilic condi-
tions where activated sludge is convertible. Here up to 13.5 times
less electricity 63 kJ was needed than required for heating (846 kJ
would be needed) to mesophilic temperatures (22 °C ? 37 °C). Or
otherwise stated the net energy in joule recovered as methane was
337 kJ, which was clearly above the 63 kJ energy input. In addition
a higher applied voltage reduces the activated sludge volume as it
increases the biogas volume.
234 M. Sugnaux et al. / Chemical Engineering Journal 324 (2017) 228–236
3.3. Inhibition of the hydrogen evolution reaction using protected
cathodes
Hydrogen evolution remained well behind expectations using
dual chambered MECs with Nafion membranes in batch mode.
One reason was that activated sludge contains only small amounts
of soluble bio-hydrogen precursors like acetate, which are easily
transformed into hydrogen and carbonate intermediates (Eq. (2)).
The carbonate equilibrium in sewage is a natural buffer and com-
peting for protons, with the possibility to decompose into CO2 and
H2O (Eq. (4)). This reduces the quantities of protons that migrated
to the cathode which can be considered as inhibition process. The
hydrogen evolution productivity was examined with variable
numbers of cathode cassettes, first with just one cathode CNaf
(Fig. 7A, see stack on the left side), and then forming stacks with
two, [A4(ACNaf)2A4] and three, [A3(ACNaf)3A4] cathodes, but hydro-
gen quantities hardly increased. With four cathodes [A3(ACNaf)4A3]
0.01 ml/day of hydrogen evolved what was a rather low quantity.
To verify, if this is equally the case when a good quantity of hydro-
gen precursors were present in the activated sludge it was spiked
with 30 g acetate and all experiments were repeated. Acetate
enhanced the hydrogen productivity slightly (Eq. (2)) to 1.3 ml
A membranes were employed in order to find a simpler and less
B not possible to obtain form the nanometer area close to the elec-
Fig. 7. Minor hydrogenesis in dual chambered MEC stacks using activated sludge
independent on the number of cathodes (CNaf) in use. A) Left side: a stack with 10
anodes and one cathode in the center [A5CNafA5] arrangement. Right side: a [A4-
(ACNaf)3A4] stack. B) Hydrogen (blue), methane (red) and CO2 (green) evolution with
the three different stacks. Hydrogen evolution was low using activated sludge and
remained low as expected even whit a three times larger cathode surface.
after 3 days of H2 using a single cathode (CNaf). The addition of
the second cathode cassette, [A4(CNafA)2A4], resulted in an
increased but still low hydrogen release. And with three cathodes
[A3(ACNaf)4A3] still only a 22.9 mL hydrogen was detected. The con-
trol experiments confirmed that hydrogen evolution was very
retarded or inhibited (Fig. 7B). The reason for this sluggish hydro-
gen evolution reaction was very likely the heterogeneous nature
of the activated sludge matrix that withheld the acetate and this
applies probably, as aforementioned, for protons as well as for
other convenient precursors for the microbial HER. Another reason
for the relatively sluggish hydrogen evolution was related to a pos-
sible hydrogen crossing over from the cathode thorough the Nafion
membrane into the anolyte [35].
CH3 COOðaqÞ þ 4H2 O ¢ 2HCO3ðaqÞ þ 9HþðaqÞ þ 8e ð2Þ
2HþðaqÞ þ 2e ¢ H2 ðgÞ ð3Þ

HþðaqÞ þ HCO3 ðaqÞ ¢ H2 OðgÞ þ CO2ðgÞ ð4Þ
3.4. Methane enrichment using polyethersulfone membrane
The methane fraction in a cathode cassette with polyethersul-
fone (PES) membrane (CPES) was unexpectedly of high purity. PES
costly membrane for dual chambered MEC processing. It also
allowed to use the anolyte as a cost free catholyte. This equally
included the premise to keep the pH close to neutral. These factors
reduce the complexity of the initially used Nafion cathode (CNaf)
what is of importance in view of a MEC scale-up. The PES mem-
brane protected the Pt-cathode form microbes as it hindered their
migration into the cathode chamber, while small particles <0.2 mm,
molecules and ions were still allowed to diffuse. This contrasted to
Nafion PEM use, were only cations, H+, Na+, K+ and the less abun-
dant Ca2+ and Mg2+, migrated with associated water molecules
[36]. With the PES a pseudo dual chambered MEC base accumula-
tion was expected to be in equilibrium with the anolyte as hydro-
xyl anions were allowed to diffuse into the anolyte and combine
with on the anode co-generated protons. Exact pH values were
trode, what is a known problematic in electrocatalysis [37].
Because methane became with time the dominant gas fraction
it was also found in the headspace of the cathode using the PES
membrane. The methane concentration in the cathode cassette
using PES membrane reached up to 96.6%. This was in contrast
with the Nafion membrane where the methane fraction was smal-
ler with 73%. The high methane concentration with the PES mem-
brane was related to the fact that hydrogen gas probably more
easily passed from the cathode into the anode than with the Nafion
membrane. But also the cathode became probably faster polluted
as ion exchange through the PES membrane was faster with the
effect that less hydrogen was produced. These assumptions were
supported by the presence of 24.5% hydrogen in the cathode cas-
sette with Nafion membrane (CNaf), while with the PES membrane
cassette only traces of hydrogen (0.41%) were detected. The rest of
the biogas fraction consisted of CO2 with 2.4% for Nafion and 3% for
the PES membrane. The PES membrane use is therefore a possible
means for in-situ methane extraction from a MEC.
3.5. Mechanistic discussion
The following excludes the common biocatalytic methanisation
of methanogens, which are not in contact or influenced by an elec-
trode. Only the reaction mechanism, which occur due to an applied
voltage are more closely examined.
 M. Sugnaux et al. / Chemical Engineering Journal 324 (2017) 228–236
The hydrogen evolution reaction (HER) in MECs is just partly
investigated for pH = 7, which is the preferred condition to main-
tain microbial activity. It was of importance to understand the
basics of the HER in this biological pH environment and to realize
model reactions. For most MEC setups in this work the HER was
considered the likely reaction at the cathode (Mechanism I). But it
was not excluded that also the bioelectrosynthetic reaction could
be involved, which was postulated as a second reaction mechanism
(Mechanism II) (Fig. 4) as the methane fraction increased with the
applied voltage. This mechanism was in particular considered for
the cathode, which was directly exposed to activated sludge. How-
ever, the examination of the reaction Mechanisms I and II in a direct
manner was not possible as activated sludge is a multi-component
substrate that contains soluble compounds that deposit on the cat-
alysts surface what turns mechanism elucidation difficult (Fig. 5).
To understand at which point the nickel plates enabled the HER
well defined model experiments were conducted at small scale in
a voltammetry setup.
At neutral pH the HER in the MEC should work well. But when
the amount of protons decreases also the cathode activity will
change.[38] Therefore the pH should be maintained at all times
at pH = 7. This quasi biological HER at the MEC cathode is the reac-
tion between electrons and protons at E° = 0.414 V to generate
H2.[39] It was concluded that the acetate based half-cell potential
E° = 0.279 V is just an idealization of what occurs in reality, visi-
ble with the acetate spiked mixtures (Table 1).
The scale-up process was performed with robust nickel plates.
To understand their activity, control experiments with nickel and
platinum electrodes at pH 7 were performed using a cyclic voltam-
metry reactor. A Tafel analysis helped to determine exchange cur-
rents (jo) with the cathodic part of the Butler-Volmer equation (Eq.
(5)). The nickel electrode’s exchange current was log(jo) = 6.10 A/
cm2, while literature reports a log(jo) = 5.2 to 5.3 A/cm2 [40]. This
showed that the neutral pH is less favorable for the HER with Ni
than under standard conditions. The exchange current for plat-
inum was log(jo) = 4.49 A/cm2 and also somewhat different from
literature values. The Tafel slopes (b) (Eq. (6)) helped to determine
rate constants k (Eq. (7)) and the activation energy for the HER (Eq.
(8)). For nickel the activation energy was Ea = 59.1 kJ/mol at pH 7,
which was clearly higher than for platinum, Ea = 34.0 kJ/mol at
pH 7. The kinetic data confirmed the expected lower hydrogen pro-
ductivity with nickel at pH = 7. This included an increased activa-
tion energy and reduced exchange currents (jo) in comparison to
alkaline electrolysis at pH = 12.
/ gF
logðjk Þ ¼ logðjo Þ þ ð5Þ
RT
g process simulation, Biores. Technol. 178 (2015) 323–329.
logðjk Þ ¼ logðjo Þ þ ð6Þ
b [16] G. Luo, I. Angelidaki, Integrated biogas upgrading and hydrogen utilization in
jo
k¼ ð7Þ
nF½Hþ 
Ea 1
lnðkÞ ¼ lnðAÞ   ð8Þ
R T
4. Conclusions
Cathode deposits in opposition to the expectation enabled the
methanisation process in a MEC. The hydrogen evolution was
inhibited or retarded using activated sludge and this also with
Nafion membrane protected cathodes. In an attempt to simplify
and improve the productivity of the dual chambered MEC the pro-
ton exchange membrane was replaced by the more porous poly-
ether sulfone membrane. With this nano-filter membrane the
235
methane fraction in the cathode increased even more and reached
up to 96.6%, while the overall methane content reached up 83.6%.
Under an applied voltage of 2.0 V the COD use of activated sludge
improved clearly to 82.6% and resulted also in significantly higher
biogas exhaust. These improvements were all possible at room
temperature. All in all, the MEC with polluted cathodes is a means
to improve the methanisation from activated sludge at room tem-
perature and represents an efficient power-to-gas technology.
Acknowledgements
This work was supported by the Fonds SIG NER of the Systèmes
Industrielles de Genève.
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