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 4 4 ( 2 0 1 9 ) 1 1 6 4 6 e1 1 6 5 4

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Effects of Nafion content in membrane electrode

assembly on electrochemical Bunsen reaction in
high electrolyte acidity

Biyi Huang, Yong He*, Yuankai Huang, Yanqun Zhu, Yanwei Zhang,
Zhihua Wang
State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, PR China

article info abstract

Article history: The electrochemical Bunsen reaction is an alternative way to traditional Bunsen reaction
Received 29 November 2018 for hydrogen production, which can produce H2SO4 and HI in lower iodine and water
Received in revised form condition in an electrochemical cell. However, energy consumption cannot be neglected
31 January 2019 due to its high electrolytic voltage. It is reported that the anode overpotential of electro-
Accepted 21 March 2019 chemical Bunsen reaction was much higher than other parts of the cell voltage. In this
Available online 10 April 2019 work, membrane electrode assemblies were prepared using a commercial 60 wt% Pt/C
catalyst by spray method. The influence of Nafion content on the electrochemical Bunsen
Keywords: reaction was studied at room temperature (298 K) by multiple electrochemical means such
Sulfur-iodine cycle as galvanostatic polarization studies, IeV measurement and impedance studies. The en-
Electrochemical Bunsen reaction ergy consumed in the electrochemical cell was calculated based on hydrogen production.
MEA preparation With the increase of Nafion content (13%e64%), the voltage and energy consumption
Nafion displayed a V-shape. The experimental results shown that the best performance was
Hydrogen production achieved with a Nafion content of 37.50% for the voltage was as low as 0.6 V and the
corresponding energy consumption was 290.5641 kJ/mol-H2.
© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

amount of energy for production nowadays with relatively

Introduction
Through continuous development and research, increasing
new energy sources start to meet the needs of human beings,
such as solar energy, wind energy, biomass, nuclear and
hydrogen. Hydrogen has more than twice the mass energy
density of typical solid fuels and hydrogen atom is the most
widely distributed substance in the universe. Hydrogen is a
kind of important secondary energy with many advantages.
However, as a secondary energy source, it requires a large
low efficiency. Therefore, seeking large-scale and cheap
hydrogen production technologies is a common concern of
scientists all over the world. Among various hydrogen pro-
duction methods, the thermochemical water-splitting
methods have attached high attention for the characteristics
of low temperature and high thermal efficiency. Among all the
thermochemical cycles, water-splitting iodine-sulfur (SI)
process is one of the most promising methods [1]. The con-
ceptual illustration of SI process was drawn in Fig. 1. The cycle
mainly includes the following three reactions:

* Corresponding author.
E-mail address: heyong@zju.edu.cn (Y. He).
https://doi.org/10.1016/j.ijhydene.2019.03.174
0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 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 4 4 ( 2 0 1 9 ) 1 1 6 4 6 e1 1 6 5 4
Fig. 1 e The conceptual illustration of SI process.
Bunsen reaction
290390K
SO2 þ I2 þ 2H2 O ƒƒƒ
ƒ! H2 SO4 þ 2HI
HI decomposition
570770K
ƒ! I2 þ H2
2HI ƒƒƒ
H2SO4 decomposition
9701270K
H2 SO4 ƒƒƒƒ! SO2 þ H2 O þ 1=2O2
The first step is the Bunsen reaction, where the SO2, I2 and
water react to form H2SO4 and HI solutions. After separation,
purification and concentration, the two acids enter the second
and third steps for decomposition respectively. The products
of SO2, H2O, and I2 can be used as cycle agent to produce acids
in the Bunsen reaction. Therefore, by processing these three
reactions, water is decomposed into H2 and O2. In order to
acquire HI and H2SO4 from the Bunsen reaction, it also re-
quires the separation of two acid solutions. A common way is
to add excess iodine in the Bunsen reaction [2]. Then the
products are naturally divided into two phases due to different
densities. But excessive circulating materials will complicate
subsequent treatment steps and increase the energy con-
sumption of the entire SI system [3e5]. Many efforts have been
done to reduce the usage of iodine and water [6]. One of the
most promising method is the use of electrochemical Bunsen
reactor which was introduced in 2004 [7].
In electrochemical Bunsen reaction, the anolyte and cath-
olyte are filled in a two-chamber electrolytic cell separated by
a proton exchange membrane. The reaction equations of
anode and cathode in electrolytic cell are shown as follows:
Anode reaction
SO2 þ 2H2 O ¼ H2 SO4 þ 2Hþ þ 2e
Cathode reaction
I2 þ 2Hþ þ 2e ¼ 2HI
H2SO4 and HI can be produced in respective compartments,
which avoids cross contamination of the two acids solution.
There is no need for further separation and purification thus
save cost. The energy consumption for the reaction was about
50% smaller by reducing the concentration of I2 [8]. It can greatly
reduce the amount of recycled materials (93% of the excess
11647
iodine and 69% of the excess water can be reduced), and the
thermal efficiency of the whole system can be as high as 42.1%
(1) [7]. Many researches on electrochemical Bunsen reactor are
under way and show that the electrochemical method is of
great potential to become an alternative of traditional Bunsen
(2) reaction. Nomura et al. found that the I2/HI mole ratio could be
reduced to 0.5 without reducing the thermal efficiency of the
system. By elevating the temperature from 313 K to 363 K, the
thermal efficiency can be further improved by 3% [9]. V.
(3) Immanuel et al. studied the effects of temperature, initial
electrolyte solution concentrations and I2/HI molar ratio on the
electrochemical Bunsen reaction with Nafion 117 membrane. It
was found that under all experimental conditions, the current
efficiency was nearly 100%, and the minimum thermal equiv-
alent required for electrolysis increased with the increase of
sulfuric acid concentration [10]. In another study, they tested
the volt-ampere characteristic curves of different I2/HI, and
discovered that the voltage increased linearly as the current
density increased, and the voltage had the lowest value when I2/
HI was 0.5 [11]. The permeability of Nafion 117 membrane was
also investigated [12]. Penetration of electrolytes still existed
even no electricity was delivered, and grew with increasing
current density. In recent years, Zhi Ying et al. have done a lot of
work on fundamental researches of electrochemical Bunsen
reaction, and confirmed an optimal operation parameter in the
range of experiment [13]. According to the research on the
transport characteristics of the proton exchange membrane,
the impurities only accounted for less than 5% of the target
product [14]. A detailed exploration on the electrode dynamics
of the electrochemical Bunsen reaction has been made, and that
both the increase of SO2 concentration in the anode and I2
concentration in the cathode were conducive to the reduction of
reaction activation energy [15]. Except these basic studies, Ravi
(4) P. proposed a new proton exchange membrane-Sulfonated
copolymer (SCP) [16]. This type of membrane exhibited high
bound water content in comparison with that of Nafion 117
(5) membrane, which indicated the SCP membranes have more
excellent stabilities in highly acidic environment.
All the researches in electrochemical Bunsen reaction were
mainly focused on changing operating parameters to achieve
optimal electrolytic effect. However, the high voltage is still a
challenge for the development of electrochemical Bunsen re-
action. The total thermal efficiency of SI system with elec-
trochemical cell (EC) was little smaller than that with the EED
11648 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 4 4 ( 2 0 1 9 ) 1 1 6 4 6 e1 1 6 5 4
equipment. In order to make the EC more competitive, the
voltage of the EC should be reduced by ca. 30% [17]. From our
previous research, the impedance of SO2 oxidized to SO2 4 in
the anode was extremely higher than that of I2 reduced to I in
the cathode [18]. As well known, the total overpotential of
electrolyzer can be separated into four components,
V ¼ Ueq þ ha þ hc þ iRA
where Ueq is the reversible cell potential, ha is the anode
overpotential, hc is the cathode overpotential and iRA is the
ohmic loss in total voltage. The most valid way to reduce the
cell voltage is reducing the anode overpotential because it is
the main constituent. Supporting catalyst layers on a proton
exchange membrane (PEM) to fabricate membrane-electrode
assembly (MEA) is a common way to reduce the activation
energy of the electrode reaction [19,20]. The catalyst-coated
membrane (CCM) method is directly coated the catalysts on
the membrane [21e23], compared with the catalyst-coated
substrate (CCS) method, the catalyst layers bind more tightly
to the PEM. Therefore, it could achieve higher catalytic activity
with lower catalyst load amount [24,25].
The catalytic layers are reaction sites, which can directly
affect the performance of the MEA. Protons, electrons and
gases are often referred to as the three phases in a catalyst
layer. The catalytic layer consists of binder and catalyst. In
addition to binding, the binder also provides proton transport
channel to electrode reaction, amplifies the three-phase re-
gion and effectively traps water to prevent membrane from
dehydration [26e29]. An appropriate transport processes in
the catalyst layers is vital for an electrochemical cell. How-
ever, excess Nafion can wrap catalyst and decrease the
porosity of catalytic layer. Therefore, it is necessary to pre-
cisely control the Nafion content in the catalyst layer to ach-
ieve the optimal balance among all the influencing factors.
As far as concerned, there is no research about reducing
the overpotential of electrochemical Bunsen reaction. In this
research, MEAs were prepared to decrease the anode over-
potential of the reaction and the optimal Nafion content in
catalyst layer was discussed. The Pt/C catalyst was selected as
the electrochemical Bunsen reaction electrocatalyst for its
outstanding catalytic activity on the electrooxidation of SO2
[30e32]. MEAs were prepared by CCM method with different
Nafion content in catalyst layers. The membranes were elec-
trochemically determined by galvanostatic polarization
studies and polarization curve measurement studies. Elec-
trochemical impedance spectroscopy (EIS) was applied to
investigate the characterization of anode catalyst in the
electrolysis reaction. The current efficiency of membrane
electrolysis was calculated by titration analysis. The experi-
mental results were evaluated by the total thermal efficiency
of SI system to produce hydrogen.
Experimental
Pretreatment of the proton exchange membrane
Nafion 115 membranes (E.I. Dupont) were first treated in 3%
H2O2 (30 wt%, Sinopharm Co., Ltd.) at 353 K for 1 h and then
treated twice with boiling 5 M H2SO4 solution and deionized
water for 30 min, respectively. The treated membranes were
preserved in deionized water.
Preparation of the catalyst ink
First, the catalyst powder (60 wt% Pt/C, Johnson Matthey) was
wetted with deionized water to prevent burning. Then the
(6) catalyst was mixed with 5 wt% solution of Nafion (E.I. Dupont).
After stirring the mixture for a few minutes, a certain amount
of glycerol was added. The weight ratio of catalyst-water-
glycerol was 1:10:22. Mix the solution by magnetic stirring
and then disperse by ultrasound for 2 h until the catalyst is
uniformly distributed and the mixture is viscous. In this work,
the weight ratio of dry Nafion: Pt were chosen as 1:4, 1:3, 1:2,
1:1, 2:1 and 3:1, corresponding to the Nafion mass fractions in
catalyst layer (N/C) of 13.04%, 16.67%, 23.08%, 37.50%, 54.54%
and 64.29%.
MEAs preparation
MEAs were prepared by CCM method with a spraying machine
(ProMax L200, Hephas Energy Co., Ltd.). Wet PEMs were fixed
in vacuum adsorption heating platform at 353 K. Applying the
catalyst ink to both sides of the membrane in multiple layers
with the catalyst loading was 0.8 mg Pt/cm2. After the catalyst
layer was coated, the membrane was naturally dried on the
heating platform for 20 min. The drying step made Nafion
more robust. The MEA was sandwiched between two
3.5 cm  3.5 cm diffusion layers (TGP-H-090, Toray) and then
this assembly was inserted into the electrolytic cell. With the
increase of Nafion content, the 6 MEAs were labeled as MEAx,
in which x ¼ 1e6 (see Table 1).
Experimental measurements
The electrochemical active surface area (ESA) of the catalyst
was measured by cyclic voltammetry in three-electrode sys-
tem. The test was carried out in 0.5 M sulfuric acid solution
which purged with N2. The working electrode was a glassy
carbon electrode with a diameter of 5 mm, the counter elec-
trode was a platinum wire electrode and the reference elec-
trode was Ag/AgCl electrode. The catalyst ink was dripped
onto the polished glassy carbon electrode and air-dried. The
Pt/C load was maintained at 40 mg. Cyclic voltammetry was
performed in the range of 0e1.2 V (vs NHE) with a scanning
rate of 50 mV/s.
The experimental setup shown in Fig. 2 were utilized to
carry out galvanostatic polarization studies and polarization
curve measurement studies of the membranes. It mainly
Table 1 e Details of membranes used in this study.
Membrane Catalyst loading (mg Pt/cm2) N/C (%)
bare Nafion 115 e e
MEA1 0.8 13.04
MEA2 0.8 16.67
MEA3 0.8 23.08
MEA4 0.8 37.50
MEA5 0.8 54.54
MEA6 0.8 64.29
 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 4 4 ( 2 0 1 9 ) 1 1 6 4 6 e1 1 6 5 4
Fig. 2 e The experimental setup of electrochemical Bunsen reaction.
consists of four parts: the anolyte and catholyte reservoirs,
recirculation section, electrochemical workstation and a two-
chamber membrane electrolytic cell. 13 mol/kgH2O sulphuric
acid saturated with SO2 was used as anolyte and 7 mol/kgH2O
HI containing I2 (I2/HI molar ratio was 0.2) was used as cath-
olyte. The H2SO4 (98 wt%) and HI (56 wt%) were purchased
from Shanghai Kefeng Industrial Co., Ltd. SO2 gas was sup-
plied into the anolyte at 20 ml/min for 2 h before the experi-
ment to ensure SO2 absorption saturation. The effective area
of the electrolytic cell was 3.5 cm  3.5 cm. The cell was
powered by an electrochemical workstation (AUTOLAB
PGSTAT302 N, Metrohm Technology Ltd.). The galvanostatic
polarization studies were lasted for 4 h at a constant current
density of 50 mA/cm2. The polarization curves were obtained
by increasing the current density incrementally every 30 s. All
membranes were activated by running the electrolyzer at
0.5 V for 30 min before the experiment was started.
The impedance studies were galvanostatically measured
at 0.3 V with a frequency response analyzer (FRA2 module)
over the frequency range of 10 mHz-10 KHz. 13 mol/kgH2O
sulphuric acid solution saturated with SO2 were fed to the
anode apartment. Replacing the catholyte with hydrogen
gas made the cathode a dynamic hydrogen electrode (DHE).
The anode acted as the working electrode and the cathode
acted as the counter electrode and the reference electrode.
Data analysis and curve fitting were processed by the soft-
ware Z-View. The test temperature was maintained at
293 K. All the tests were carried several times until there
were no significant changes.
Calculations of current efficiency and energy consumption
Electrochemical reactions which involve the conversion of
electrical energy into chemical energy, are generally assessed
by current efficiency. According to Faraday's law, when the
electric quantity passing through the electrolytic cell is Q (C),
the relationship of moles of the product (N) and the current (I) is:
It ¼ Q ¼ nFN
11649
I, t, and F denote the current (A), the electrolysis time (s) and
the Faraday constant (96,485 C/mol), respectively. n is the
number of electrons needed to generate each mole of HI. In
this reaction, n is defined as 1. Hence, the theoretical amount
of HI produced during the electrolysis is:
N ¼ It=F (8)
The current efficiency is calculated by the ratio of the
actual mole quantities change of HI to the theoretical
mole yield of HI during the electrolysis [33]. It is described
as:

hcI ¼ DNcHI N (9)
DNcHIis the change of the HI molar quantities of the
cathode electrolyte before and after the reaction, obtained
by titrating the I before and after the experiment. N is
the theoretical yield of HI calculated based on charge
supplied.
Since the aim product of the SI cycle is H2, the energy
consumed in the electrochemical process should be based on
hydrogen production. U is the heat equivalent of the electric
energy consumed to produce 1 mol of H2 and is calculated by
Eq. (10) [33]:


UH2 ¼ 2FVe hE hcI (10)
where Ve is the average cell voltage (V) during electrolysis, F is
the Faraday constant, hcI is the thermoelectric conversion
efficiency of thermal power plant, assuming 0.4 and hE is the
cathode current efficiency.
Results and discussion
Cyclic voltammetry analyses
Fig. 3 shows the cyclic voltammograms of Pt/C catalyst with
different Nafion contents. The ESA of Pt particles was calcu-
(7) lated by the following formula:
11650 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 4 4 ( 2 0 1 9 ) 1 1 6 4 6 e1 1 6 5 4

Table 2 e The calculated ESA data.

N/C (%) ESA (m2/g)
13.04 51.72
16.67 61.80
23.08 68.70
37.50 78.56
54.54 74.91
64.29 73.44

Current-voltage characteristics studies

Fig. 5(a) shows the current density-potential curves of MEAs

with different Nafion loading. The rising trend of the cell
Fig. 3 e Cyclic voltammograms for different Nafion content voltage leveled off when the MEA was applied. It can be seen
of the catalyst layer. that the performance increased with dry Nafion content up to
37%, and decreased afterwards. The polarization curves could
be divided into three regions: electrochemical activation re-
gion (at a current density less than 10 mA/cm2), ohm region
(10e60 mA/cm2) and concentration polarization region
QH ðmCÞ
ESA ¼ (11) (>60 mA/cm2). The gentle curve after 1.8 V might due to the
210ðmC=cm2 Þ  MPt ðgÞ
oxidation of the carbon substrate. At low current density, the
where QH is the electric quantity of the adsorption peak, overpotential is mainly used to overcome the activation en-
calculated by integrating the area of the adsorption- ergy of the reaction, namely electrochemical polarization. In
desorption peak of hydrogen in the potential range of the region of current density between 10 and 60 mA/cm2, the
0e0.4 V (vs NHE). 210 mC/cm2 is the specific charge related potential was high enough to promote the electrochemical
to monolayer adsorption of hydrogen on polycrystalline reaction but the reaction was not yet affected by mass trans-
platinum (see Table 1). M is the Pt loading on the glassy fer. In this case, the reaction was dominated by electro-
carbon electrode. The calculated ESA data are listed in chemical polarization and ohmic polarization. The ohmic
Table 2. The ESA increased and then decreased with the polarization was mainly due to the resistance of electrons
increase of Nafion. The increase of ESA in the early stage transferred between the electrodes and the reactants or the
indicated that the three-dimensional catalytic layer was products. As the difference of reactants concentration be-
gradually formed. The decrease of ESA in the later stage tween electrode surface and electrolyte became larger, the
reflected the blockage of catalyst particles due to excessive reaction enters the concentration polarization region (current
Nafion ions. density>60 mA/cm2). For the test with bare Nafion 115 mem-
brane, the electrochemical resistance was considerably high
Galvanostatic polarization studies and the cell potential grew quickly with current density
increasing. To present the experimental results more
Fig. 4 shows the evolution of cell voltage in constant-
current electrolysis with different MEAs. Under the same
test conditions, the cell voltage was reduced by 56.35% after
the catalyst was added, reduced from initial 1.37 Ve0.6 V.
Large decreases were observed when the Nafion content
was increased from 13.04% (MEA1) to 37.50% (MEA4). Low
Nafion loading led to a reduction in the performance which
can be proved by the uptrend in voltage of MEA4-MEA1. E.A.
Ticianelli proposed as early as 1988 that introducing an
alcohol solution of a perfluorosulfonic acid electrolyte (such
as Nafion) into the electrode preparation can extend three-
phase region of the electrode [34]. More than the ratio of
37.50%, the change became much less. Deserve the curves
of MEA4 to MEA6, an increase in voltage indicated that the
electrode with Nafion content over 37.50% had a slightly
worse performance which was consistent with ESA results.
Since Nafion is a poor conductor of electrons, it reduced the
conductivity of the catalytic layer and caused the particles
to be isolated from each other. These isolated catalyst
Fig. 4 e Evolution of cell voltage during electrolysis for the
particles do not participate well in electrochemical
investigated Nafion loading at current density of 50 mA/
reactions.
cm2.
 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 4 4 ( 2 0 1 9 ) 1 1 6 4 6 e1 1 6 5 4 11651

of current density. As shown in Fig. 5(b), the voltage of

MEA4~MEA6 increased with the increase of Nafion content,
indicating excess Nafion would lead to the decrease of elec-
trolytic cell performance. MEA with dry Nafion content was
37.50% showed the optimal electrochemical Bunsen reaction
performance as it had the minimum voltage under the same
current density.

EIS studies

The equivalent circuit diagram shown in Fig. 6(a) was

composed of different electrochemical elements. The equiv-
alent circuit was divided into three parts, which are ohm
impedance (Rm), charge transfer resistance (Rct) and constant
phase element (CPE), respectively. Rm was mainly caused by
membrane resistance, including contact resistances between
components and resistance of individual components such as
the PEM, catalyst layers, gas diffusion layers and graphite
plates. Rct was called charge transfer resistance, which was
mainly caused by the impedance of the charge conduction in
the catalytic layer during the cell reaction process. Since the
capacitance of porous electrode was distributed along the
pore length, CPE was used to replace the conventional double-
layer capacitance. The Nyquist plots in Fig. 6(b) were approx-
imately semicircles. The arc radius represented the charge
transfer impedance in the electrolytic process, while the
intersection point between the high frequency area of the
curve and the X-axis was the ohmic impedance of the elec-
trolytic system.
Fit the impedance curves by the simple equivalent circuit
drawn in Fig. 6(a) and the calculated Rm and Rct were listed in
Table 3. In the test group without catalyst, the anode

Fig. 5 e (a) Current-voltage characteristics of electrolytic

cell at different membranes. (b) Nafion contents versus cell
voltage at various current density.

intuitively, the cell voltage under different current densities is

plotted in Fig. 5(b) with Nafion load as the X-axis. As can be
seen from the figure, all curves were similar in shape and the
lowest voltage was reached when the Nafion content was
37.50%. When the content of Nafion exceeds 37.50%, the per-
formance of the electrolytic cell does not change much with
current density. Examining the electrochemical polarization
region of IeV curves, it was noticed that all the MEAs were
comparable. The influence of Nafion load is more obvious
when the current density above 60 mA/cm2, especially in the
case of very small amount of Nafion. From MEA1 to MEA4, the
decrease in cell potential indicated the formation of optimal
three-phase reaction interface. First, the catalysts were in bad
contact with Nafion led to the increase in proton transfer
resistance. Second, the continue protons conduction in cata-
lyst layers was likely to be interrupted. The higher the current
density, the more protons were required to be produced and
transferred. The number of protons were not enough to ser- Fig. 6 e (a) Equivalent circuit of the anode reaction. (b)
vice the request at certain current density. Therefore, the Nyquist plots of the anode impedance test with H2 gas
voltage difference of MEA1~MEA4 increased with the increase supply to cathode.
11652 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 4 4 ( 2 0 1 9 ) 1 1 6 4 6 e1 1 6 5 4

which made more catalysts participated in the effective

Table 3 e Data of anode impedance calculated by the
electrode reaction. According to the polarization curve test
equivalent circuit.
(Fig. 6(a)), proper Nafion resin loading could reduce the diffu-
Membrane Rm（U） Error/% Rct（U） Error/%
sion resistance of the membrane electrode and improve the
4
bare Nafion 115 7.368 3.867 2.65  10 2.106 electrochemical performance of the MEA in the polarization
MEA1 1.339 1.451 28.79 1.201 curve.
MEA2 1.002 1.166 25.07 1.239
MEA3 0.9925 1.291 19.27 1.564
MEA4 1.031 0.674 16.18 1.557 Calculation of current efficiency and energy consumption
MEA5 1.252 0.730 19.86 0.441
MEA6 2.082 0.824 22.23 0.585 The cathode current efficiency and energy consumption of
various membranes during the 4 h constant current electrol-
impedance was as high as 2.65  104 U. However, the Rct of the ysis process were calculated by using Equations (9) and (10).
MEAs were significantly reduced, only about 20 U, which The calculated data were listed in Table 4. For 4 h electrolysis,
indicated that Pt/C catalyst could decrease Rct and promote from MEA1 to MEA4, the current efficiency with the Nafion
electron transfer reaction. The data showed that Rm of content increasing and from of MEA4~MEA6 it was nearly
Nafion115 membrane experimental was as high as 7.368 U, 100%. On the basis of the current efficiency formula (Eq. (10)),
while the value was reduced to about 1 U after applying since the current, time and Faraday constant were all equal,
catalyst. It was because the carbon paper can also be used as the reason for the current efficiency change was only the yield
the electrode to reduce the distance between the solution and of the target product. The target product of this experiment
the electrode. With the increase of the content of Nafion was HI. The permeated SO2 4 and SO2 was reduced to S and H2S

polymer in the catalytic layer, the ohmic resistance of the on the cathode electrode by consuming part of the electrons
electrode changed slightly, but the trend was first to decrease used for I2 reduction reaction. Moreover, with SO24 and SO2 in

and then to increase. Current studies shown that the catalytic
layer containing Nafion ionomer is a mixed heterogeneous
conductor, which can conduct both electrons and ions
[35e37]. Since the Nafion ionic polymer can transport Hþ in
the catalytic layer, low levels of Nafion could lead to some
negative effects due to the discontinuity of Nafion phase in the
catalytic layer. On the other hand, a considerable number of
catalysts are unable to contact with Nafion polymers to form
an effective three-phase reaction interface, leading to a
reduction in catalytic activity. Therefore, the electrode had
high ion resistance and electrochemical reaction resistance.
However, Nafion is an electrically non-conductive material.
The addition of too much Nafion could cause some of the
catalysts to be completely wrapped and insulate them. The
catalysts become less efficient because excess Nafion in-
terdicts the transport channel of electron and reactant. In
consequence, the ion resistance of the electrode decreases
with the increasing of Nafion content, while the electronic
resistance increases. There must be an optimal Nafion content
that makes MEA the best electrochemical performance. It can
be seen from the results that when Nafion content was 37.50%
(MEA4), the MEA possessed a relatively smaller Rm and Rct. It
showed that MEA4 had an excellent electrode structure,
cathode electrolyte some side reactions might occur with HI,
which had been mentioned in the research of Nomura and Zhi
Ying [13]. The main side reaction equations include:
H2 SO4 þ 6HI/S þ 3I2 þ 4H2 O (12)
SO2 þ 4HI/S þ 2I2 þ 2H2 O (13)
In the side reaction, HI is constantly consumed. All these
factors would lead to a decrease in the production of cathode
HI. It was clearly observed that at the end of the experiment
using Nafion 115 membrane, the solution in the anode storage
tank became reddish brown, and there were a large number of
yellow solid attachments on the cathode side of the mem-
brane and the cathode carbon plate. The reddish brown ano-
lyte was due to the permeated I2 from catholyte and the yellow
solid was because S generated from the side reaction. After
the addition of the catalytic layer, the solution in the anode
reservoir became lighter and the production of S in cathode
side decreased, indicating that the permeation of the two so-
lutions decreased because of the thickening of the membrane.
The energy consumption to produce 1 mol of hydrogen
decreased firstly and then increased with the increase of
Nafion content. The little increases of energy consumption in

Table 4 e Some related data of membranes performance in the constant-current electrolysis. The initial concentration of
anode H2SO4 was 13 mol/kgH2O, the cathode HI concentration was 7 mol/kgH2O, the molar ratio of I2/HI was 0.2, and the
current density was 50 mA/cm2.
Membrane Initial HI conc. Final HI conc. Final I2/HI Average Cathode current Energy consumption kJ/
(mol/kg) (mol/kg) ratio voltage (V) efficiency (%) mol-H2
bare Nafion 3.109 3.620 0.269 1.37 63.16 1084.546
115
MEA1 3.146 3.727 0.075 0.976 71.77 655.818
MEA2 3.142 3.775 0.078 0.886 78.22 546.417
MEA3 3.145 3.832 0.066 0.868 84.88 493.591
MEA4 3.142 3.945 0.045 0.598 99.29 290.5641
MEA5 3.153 3.956 0.045 0.630 99.20 306.387
MEA6 3.154 3.957 0.046 0.651 99.30 316.214
 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 4 4 ( 2 0 1 9 ) 1 1 6 4 6 e1 1 6 5 4
MEA5 and MEA6 were resulted from the higher cell voltage. A
best performance was reached at MEA4 for it had the lowest
the energy consumption of 290.5641 kJ/mol-H2. The decrease
was 73.21% compared to 1084.546 kJ/mol H2 using bare
Nafion115 membranes.
Conclusion
In order to study the influence of Nafion content in membrane
electrode on the electrochemical Bunsen reaction, 6 MEAs
with different Nafion content were prepared using 60 wt% Pt/C
catalyst. The study demonstrated that MEA effectively
reduced the voltage of the electrochemical Bunsen reaction
and obtained better electrolysis effect than bare Nafion 115.
Nafion in catalyst layers will change the porosity, perme-
ability, and hydrophobicity of the catalyst layer. Proper Nafion
content enables the catalytic electrode to form an effective
three-phase reaction interface, reducing the transfer resis-
tance of reactants, electrons and protons. In the electro-
chemical Bunsen reaction, a Nafion content of about 37% of
the total catalyst layer weight appeared to be optimal to
minimize charge transfer resistance. The best catalytic per-
formance was obtained with the lowest electrolytic voltage of
0.596 V (56.35% lower than using Nafion 115 membranes
alone) and the lowest energy consumption of 290.5641 kJ/mol
H2 (73.21% lower than that of bare Nafion115 membrane). In
terms of energy consumption, the SI system with electro-
chemical Bunsen reactor can be comparable to that with the
EED equipment. However, Pt is a rare and expensive metal,
seeking cheap metals or composite catalyst to substitute
noble metal like Pt has always been a major goal. Future works
will focus on catalyst design to offer significant cost savings
and enhance the commercial feasibility of the electrochemical
Bunsen reaction.
Acknowledgement
This work was supported by the Innovative Research Groups
of the National Natural Science Foundation of China
(51621005) and Program of Introducing Talents of Discipline to
University (B08026).
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