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Synthesis and ex‐situ evaluation of quaternized polysulfone as an anion

exchange ionomer for AEM technologies

Article in Journal of Applied Polymer Science · November 2022

DOI: 10.1002/app.53359

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Received: 22 June 2022 Revised: 16 October 2022 Accepted: 23 October 2022
DOI: 10.1002/app.53359

RESEARCH ARTICLE

Synthesis and ex-situ evaluation of quaternized polysulfone

as an anion exchange ionomer for AEM technologies

Luis J. Salazar-Gastélum 1
n-Gastélum 1

| Mara Beltra |
Julio C. Calva-Yañez 2
| Shui Wai Lin | Daniel Cha
vez-Velasco 1 |1

Moisés I. Salazar-Gastélum 1,3 | Sergio Pérez-Sicairos 1

1
Tecnol
ogico Nacional de México/IT de
Tijuana/Centro de Graduados e Abstract
Investigaci

on en Química, Tijuana, Anion exchange ionomer (AEI) is a critical component used on anion
Mexico
exchange membrane fuel cell (AEMFC) and alkaline water electrolyzer
2
CONACyT-Tecnol
ogico Nacional de
(AWE). In this work, quaternized polysulfone with different functionalization
México/IT de Tijuana/Centro de
Graduados e Investigaci

on en Química, degree were used as an ionomer to evaluate the performance in the oxygen
Tijuana, Mexico reduction reaction (ORR) and hydrogen oxidation reaction (HOR), both
3
Tecnol

ogico Nacional de México/IT de implied in the operation of AEMFC and AWE. The synthesized ionomer
Tijuana/Posgrado en Ciencias de la
Ingeniería, Tijuana, Mexico exhibited a better performance in both reactions in comparison to the commer-
cial AEI Aemion®. PSf-130 exhibited better performance, since IEC and sur-
Correspondence
face area increases twice regarding the same parameters in the PSf-60. The
Moisés I. Salazar-Gastélum and Sergio
Pérez-Sicairos, Tecnol

ogico Nacional de PSf-130 conductivity increases three times regarding the value exhibited by
México/IT de Tijuana/Centro de PSf-60. Finally, the Jlim and Jk increases 67% and 100% for ORR. On the other
Graduados e Investigaci
on en Química,
hand, the same catalytic parameter increased 44% and 35% for HOR compar-
Tijuana, BC, 22510, México.
Email: sergio.perez@tectijuana.edu.mx ing both polysulfone-based ionomers. The Tafel slope values do not showed
and moises.salazar@tectijuana.edu.mx drastically changes for different ionomers indicating the same rate determining
Funding information
step (RDS) and the same mechanism in both reactions for all the ionomers.
Consejo Nacional de Ciencia y Tecnología,
Grant/Award Numbers: 786162, INFR- KEYWORDS
2011-3-173395; Tecnol
ogico Nacional de anionic exchange ionomer, electrolyzer, fuel cell, HOR, ORR
México, Grant/Award Numbers:
14234.22-P, 11377.21-P, 11326.21-P

1 | INTRODUCTION requirements of the grids. Therefore, the storage of surplus

The main strategy for the energy global policies consists
on the incorporation of clean electrical energy from renew-
able resources in the electrical energy network to decrease
the dependence upon fossil fuels. However, the generation
rate for renewable resources is relatively unpredictable,
because it depends upon several factors, such as the season,
the weather, orography, and the availability of the resource
(tidal, wind, solar, chemical, etc.).1,2 Supplying of the
renewable energy in the electrical grid is a difficult task,
because the generation/conversion rates rarely match the
electricity is a very important aspect for the management of
the electrical energy supply. Electrical energy cannot be
stored for long periods of time, however, it can be trans-
formed into mechanical and chemical energies and stored
them for later usage, besides the devices for the storage of
electrical energy (capacitors and supercapacitors) possess
range values from 10
2 s to 102 s. From the mechanical
point of view, compressed air and hydro storage systems are
the main options commercially available.3,4 Additionally,
chemical storage of electrical energy involves several
devices, such as batteries, electrolyzers, and fuel cells.5–7

J Appl Polym Sci. 2023;140:e53359. wileyonlinelibrary.com/journal/app © 2022 Wiley Periodicals LLC. 1 of 11

https://doi.org/10.1002/app.53359
2 of 11
Among fuel cell technology, solid oxide fuel cell
(SOFC),8 enzymatic fuel cell (EFC),9 proton exchange
membrane fuel cell (PEMFC)10 and anionic exchange
membrane fuel cell (AEMFC)11 are few of the technolo-
gies currently in development. From those devices,
PEMFC and AEMFC emerge as the most attractive
options, owing to their low operation temperature and
flexibility of the fuel, etc. The reactions taking place in
those devices are the oxygen reduction reaction (ORR,
Equation 1) and the hydrogen oxidation reaction (HOR,
Equation 2) at the cathodic and anodic compartments,
respectively. Both reactions take place at the triple-phase
boundary (ionomer-catalyst-electrolyte, TPB). The main
difference between the AEMFC and PEMFC is the ion
transference in the process occurring through the iono-
mer and the membrane.
O2 þ 2H2 O þ 4e
! 4OH
E ¼ 0:40V ð1Þ
2H2 þ 4OH
! 4H2 O þ 4e
E ¼
0:83V ð2Þ
The mechanisms for ORR and HOR are mainly explained
by Koutecky-Levich (KL) analysis. ORR and HOR are
diffusion-limiting processes, where the inverse of current
density varies linearly to the inverse of the square root of
the rotation rate of the electrode under hydrodynamic
conditions, accordingly to Equation (3):
1 1 1 1 1 commercial ionomer Nafion®, authors pointed out that gas
¼ þ ¼ þ ð3Þ
j jk jd jk BC 0 ω1=2
Moreover, the rate determining step (RDS) is associ-
ated with the Tafel slope value. For Pt-based catalyst in
the HOR, the Tafel slope value of 30 mV dec
1 is
ascribed to the dissociative hydrogen adsorption step as
the RDS (Tafel step, Equation 4). On the other hand,
Tafel slope value of 120 mV dec
1 is associated to the
electronic charge transfer (either via Heyrovsky step or
Volmer step, Equations (5) and (6), respectively).12–14
!
H2 þ 2M 2M
Hads ð4Þ
!
H2 þ OH
þ M M
Hads þ H2 O þ e
ð5Þ
! Shrivastava and coworkers reported the evaluation of
M
Hads þ OH
M þ H2 O þ e
ð6Þ
The nature and loading of the ionomer solution are
considered key aspects in the fuel cell and electrolyzers
applications, since the ionomers bring mechanical stabil-
ity and also the ionomer acts as a pathway for hydroxide
ion transfer to perform the reactions at the catalyst sites
in the TPB.15,16 Usually, the research works focus on the


SALAZAR-GASTELUM ET AL.
effect of the catalytic layer and the membrane, but the
effect of the ionomer is neglected and/or dismissed.17,18
Most of the works reported the usage of PTFE as a
binder in the TPB, however, PTFE is not considered an
ionomer, since no ion conductivity is shown, acting only
as a binder.19 Currently, the most known ionomer for
PEMFC technology is Nafion® from DuPont™, this iono-
mer exhibits excellent performance as an ionomer, since
the good mechanic stability at acidic and alkaline condi-
tions and high ion conductivity, however, the depen-
dence of the ionomer technology towards commercial
products limits the development of the devices. In recent
years, there is an ongoing research on several new iono-
mers, specifically for alkaline conditions, such as FAA-3
from Fumatech™, this is an ionomer reported for OH

conductivity, nevertheless, research works in novel iono-
mers for alkaline conditions and is widely addressed in
last few years.
Cho et al. reported the effect of the ionomer loading
on the performance of the PEMFC by using the commer-
cial ionomer Aquivion®, authors stated that HOR and
ORR take place in the catalytic layer, which implies that
ionomer influences the performance of the PEMFC, how-
ever, the study does not exhibit the analysis of the mech-
anism in those reactions, demonstrating the performance
at the PEMFC only.20
Similarly, Jeon et al. reported the effect of ionomer
loading on the performance of the PEMFC by using the
transport through the catalytic layer is highly influenced by
ionomer loading, nonetheless, the study does not provide
any evidence of changes in the mechanism of the reaction
that occurs during the energy conversion process.21
The commercialization of AEMFC requires the develop-
ment of new anionic exchange membranes and anion
exchange ionomers to enhance the ionic conductivity in the
TPB. Several polymers have been studied for preparing the
backbones for ionomer solution, such as polysulfone (PSf),22
polyphenol oxide,23 polyether etherketone (PEEK),24 polyvi-
nyl alcohol (PVA)25 and polysterene.26 Alternatively, the
modification of the backbone with cationic groups like
phosphonium,27 quaternary ammonium,28 guanidine29 and
imidazolium30 functional groups have shown to enhance
the ionic conductivity.
an ionomer based in quaternary polyphenol oxide com-
pared to the commercial FAA-3 ionomer. The authors
found that the quaternary polyphenol oxide possesses a
higher hydration number which increases the conductiv-
ity compared to the FAA-3 ionomer.31 Regarding the
evaluation of ionomers, our research group has experi-
ence in the evaluation of ionomers for AEMFC
applications.32


SALAZAR-GASTELUM ET AL.
Chae et al. prepared hydroxide-ion-conducting elec-
trode ionomers based on quaternary-ammonium group-
functionalized polystyrene (PS) with variable molecular
weights and side chain length, the ionomers were synthe-
sized by radical polymerization of styrene followed by
acylation, reduction, and quaternization. The ionomers
were evaluated in anion-exchange membrane fuel cells
(AEMFCs), obtaining a maximal power density of
407 mW cm
2.16 Furthermore, Nivedha et al. reported
anion and cation conducting polymers, hydrophilic and
hydrophobic polymers as the air electrode of an alkaline
zinc-air battery (ZAB). The highest performance was
obtained with Fumion® ionomer (current density of
about 163 mA cm
2 at 0.6 V) owing to the right propor-
tion of hydrophilic-hydrophobic segments and ion-
conducting nature. A specific capacity of 770 mA h g
1
was obtained when Fumion® was employed as a binder
with 1 mg Pt cm
2.33 Additionally, Spanos et al. studied a
polymeric ionic liquid used as a binder to formulate
nanoparticulate water oxidation catalysts and create a
highly active and stable electrode, highest performance
was shown with poly(ionic liquid) (PIL) as a binder for
NiCo oxide nanopowder, improving the activity and
cycling stability.34
In this work, PSf was modified with quaternary
amine to obtain quaternized PSf-based ionomers with
different functionalization degree. The prepared iono-
mers were characterized by physicochemical techniques
and then evaluated for ORR and HOR catalysis in alka-
line media, studying the effect on the mechanism and
the kinetic parameters for both reactions. Although
there are few reports about the nature of the ionomer
and its influence on the performance of the AEMFC/
PEMFC and/or electrolyzers, the mechanism and
changes in the rate determining step of the reactions
have not been formally discussed, which is the main
topic of this work.
2 | MATERIALS AND METHODS
2.1 | Synthesis of the polymers
Ten grams of PSf pellets (Sigma Aldrich, Mw 35,000) was
dissolved in chloroform (Meyer, 99.8%) under magnetic
stirring in a round bottom flask. Then, 6 g of paraformal-
dehyde (Sigma Aldrich, reagent grade) was added, after-
wards, 700 μl of tin chloride (IV) (Sigma Aldrich, 98.0%)
was added dropwise to the suspension. Finally, 30 ml of
chlorotrimethylsilane (Sigma Aldrich, 98.0%) were added
dropwise following the methodology reported by Avram
and co-workers.35 The different functionalization degree
(60% and 130%) were obtained by varying the reaction
3 of 11
time during the chloromethylation reaction (20 and
48 h). Once the reaction has finished, the solution was
precipitated into cold methanol under stirring, the pre-
cipitated PSf functionalized with CH2Cl groups (PSf-Cl)
was filtered and washed several times with methanol and
dried at 50 C in a vacuum oven. Those precursors with
different functionalization degree were used for quaterni-
zation reaction, 1.5 g of the PSf-Cl was dissolved into
N-methyl-pyrrolidone (NMP) (Sigma Aldrich, 99.0%) by
magnetic stirring in a round bottom flask, then 1 ml of
triethylamine (TEA) (Sigma Aldrich, 99.0%) was added
and then the mixture was refluxed at 80 C for 24 h, to
replace the Cl with the amine groups. The solution was
precipitated in diethyl ether (Fermont, anhydride grade)
several times and washed with ethyl acetate (Fermont,
99.5%). A brown powder (PSf-N) was obtained and stored
in a vacuum oven at 40 C.
2.2 | Characterization
1
H NMR spectra of the synthesized polymers were
recorded at 400 MHz with a Bruker Advance III HD spec-
trometer at 30 C, chemical shifts were referenced to the
peak of tetramethylsilane (TMS) and the polymers were
dissolved in chloroform-d (Sigma Aldrich, 99.8%).
FT-IR spectra were recorded with a Perkin Elmer
Spectrum 400 instrument with attenuated total reflec-
tance at a scanning range of 600–4000 cm
1, with a reso-
lution of 2 cm
1 and 16 scans.
Thermogravimetric analysis (TGA) was performed
under a nitrogen atmosphere (60 L min
1) with a TGA
Q500 TA Instruments. The thermogravimetric curves
were recorded in a temperature range from 30 to 800 C
and a heating rate of 20 C min
1.
For the water uptake, the dried polymer samples were
weighed and then immersed in distilled water at room
temperature for 24 h. The hydrated polymer was taken
out and the excess of water was removed and weighed
immediately.
For ion exchange capacity (IEC) and anionic conduc-
tivity (σ), polymers were used in form of a polymeric film
as a previous report.36 Doctor blade technique was used to
prepare the thin film. Briefly, 10 g of polymeric solution
(polymer content 16 wt%) in NMP was prepared for each
polymeric film. The polymeric solution was poured onto a
clean glass plate placed at the membrane casting device
(lab-made) using a gap of 0.53 mm. Afterward, the glass
plate/solution film was placed into a convection oven at
30 C for 24 h to remove the solvent in a controlled envi-
ronment. Finally, the membrane was removed from the
glass plate by immersing it in deionized water at room
temperature. IEC determination was carried out by an
4 of 11
acid–base back-titration using phenolphthalein as an indi-
cator as reported by Wan and co-workers,37 while the
anionic conductivity (σ) was measured with electrochemi-
cal impedance spectroscopy (EIS), using a four-probe
H-cell configuration. EIS was measured in the frequency
range of 1 MHz to 10 Hz, with a potential amplitude of
10 mV, using BioLogic VMP-300 potentiostat/galvanostat.
Platinum plates (1 cm2) were used as working electrodes
and Ag/AgCl as a reference electrode. A solution of 1.0 M
NaOH was used as an electrolyte, membranes coupons
(4 cm2) were placed between the two compartments of the
H-cell. The σ was estimated accordingly to Equation (7).
L grams were recorded from
1.0 to 0.7 V in 0.1 M NaOH
σ¼ ð7Þ
Rmem A
where σ is the anionic conductivity (mS cm
1), Rmem is
the value obtained between the difference of the cell
filled only with electrolyte without membrane (blank
signal) and cell with membrane (Rmem + electrolyte), L is
the thickness of the membrane (cm), and A is contact
area of membrane with electrolyte solution (cm2). All the
membrane measurements were performed at room
temperature.
The Surface area of the synthesized polymers was
determined by BET analysis using a Quantachrome
Instrument, model autosorb iQ, the BET data analysis
was processed using the Quantachrome ASiQwin
software.
Energy dispersive X-ray (EDX) spectroscopy analysis
of PSf-N polymers was carried out using a Bruker XFlash
4010 EDX detector attached to a TESCAN VEGA3
Scanning Electron Microscope (accelerating voltage of
10 kV). EDX information was processed using Quantax
200 ESPRIT 1.9 software.
2.3 | Ionomer solution preparation ORR
and HOR catalytic activity
Ionomer solutions were prepared by dissolving the ade-
quate amount of PSf-N polymer in NMP under magnetic
stirring and were diluted to 2.5 wt% using a solution of
water/methanol/isopropyl alcohol (1:1:1). The catalytic
inks were prepared as reported elsewhere38,39 using the
commercial catalyst Pt/C 10 wt% (Fuel Cell Store), but
instead Nafion®, the ionomer solutions based on PSf-N
were used. The evaluation of the catalytic activity for
ORR and HOR was performed in a typical three-electrode
cell, with a glassy carbon rotating disk electrode
(GCRDE, 0.2 cm2 of geometric area) modified with the
catalytic inks as the working electrode, a Hg/HgO/KOH
1.0 M as reference electrode, and a Pt coil was used as


SALAZAR-GASTELUM ET AL.
the counter electrode. Electrodes were immersed in a
solution of 0.1 M NaOH and the polarization curves for
ORR and HOR were performed at the potentiostat/
galvanostat Biologic model VMP-300. All potential values
were referred to as the RHE (Reversible Hydrogen
Electrode). Before each electrochemical measurement,
the working electrode was activated by imposing 30 cyclic
voltammograms in the potential range of
1.1 to 0.7 V in
0.1 M NaOH saturated with N2 at a scan rate of
100 mV s
1. Afterward, for ORR studies, linear sweep
voltammograms were recorded from 0.4 to
1.0 V in
0.1 M NaOH saturated with O2 and a scan rate of
5 mV s
1. On the other hand, linear sweep voltammo-
under saturated a hydrogen atmosphere at scan rate of
10 mV s
1 for the HOR catalytic studies. In both cases,
polarization curves for ORR and HOR were executed
under hydrodynamic condition, in order to evaluate the
catalytic activity and the mechanism of both reactions.
The pathway of the whole experimental design is shown
in Scheme 1.
3 | RESULTS A ND DISCUSSION
3.1 | Physicochemical characterization
of ionomers
Figure 1 shows 1H NMR spectra for PSf (a) and PSf-Cl
(b) with different functionalization degree. Spectra for
PSf showed peaks corresponding to isopropyl of the main
chain and phenyl groups at 1.8 ppm and 7–8 ppm,
respectively, where the hydrogens close to the sulfone
group appear at 7.9 ppm. The 1H NMR spectrum of the
PSf-Cl shows a new peak at 4.5 ppm (Hf), corresponding
to hydrogens from the chloromethyl moiety incorporated,
as well new chemical environment to the aromatic
hydrogens. The amount of CH2Cl incorporated into the
backbone of PSf was calculated from 1H NRM spectrum
of PSf-Cl accordingly to Pérez-Prior (Equation 8)40:
AH f=2
DC ¼  100 ð8Þ
AH e=6
where DC is the degree of chloromethylation, AHf is the
integration value for two hydrogens (methylene group) at
4.56 ppm, and AHe corresponds to the integration for six
hydrogens (isopropyl group) at 1.8 ppm.
Figure 1c shows the 1H NMR spectrum in DMSO-d6 for
the quaternized PSf, where it is observed that the signal cor-
responding to the methylene, shifts to lower ppm values in
the quaternary ammonium derivative (4.43 ppm), also is
observed another signal at 4.37 ppm and it is attributed to


SALAZAR-GASTELUM ET AL. 5 of 11

S C H E M E 1 The experimental sequence of this research: (1) chloromethylation of PSf, (2) quaternization reaction with TEA for PSf-x-N,
(3) stock solution preparation with NMP, (3a) thin film preparation, (3b) dilution of stock solution to 5 wt.% and (4) dilution with mix
solvent for the ionomeric solution. [Color figure can be viewed at wileyonlinelibrary.com]

F I G U R E 1 1H NMR spectra
for (a) PSf, (b) PSf-Cl, and
(c) PSf-N. [Color figure can be
viewed at
wileyonlinelibrary.com]

an incomplete functionalization, because this signal corre- methyls, as previously reported.40 Two quaternized PSf
sponds to unreacted chloromethyl group. It is important to were prepared, PSf-60-N obtained from PSf-Cl with a DC of
point out that the new signals for the triethylamine moiety 60% and PSf-130-N obtained from PSf-Cl with a DC
appears at 3.2 ppm for methylenes and at 1 ppm for of 130%.
6 of 11
F I G U R E 2 (a) FT-IR spectra of PSf and PSf-Cl; and (b) FT-IR spectra of PSf-60-N and PSf-130-N. [Color figure can be viewed at
wileyonlinelibrary.com]
F I G U R E 3 Thermograms of pristine PSf and modified PSf.
Heating rate: 20 C min
1 and nitrogen atmosphere [Color figure
can be viewed at wileyonlinelibrary.com]
Figure 2a shows the FT-IR spectrum of the PSf and PSf-
Cl, the peak at 2968 cm
1 corresponds to aliphatic stretching
C H from isopropyl groups of the backbone of PSf, the peak
located at 1150 cm
1 corresponds to the symmetric stretch-
ing of the sulfone group. Besides, an asymmetric stretching
of sulfone group is observed at 1320 and 1296 cm
1. Finally,
other signals are shown at 1238 and 1012 cm
1, attributed to
asymmetric stretching (C O C).41,42 The sharpest band
located at 757 cm
1 for PSf-Cl spectra than bare PSf is attrib-
uted to C Cl (inset of Figure 2a). This is consistent with 1H
NMR, showing that PSf-Cl was obtained by aromatic nucleo-
philic substitution.43


SALAZAR-GASTELUM ET AL.
The presence of quaternized ammonium groups was
confirmed by FT-IR in Figure 2b. The inset shows an
absorption peak at 3200 cm
1 attributed to the OH bonding
of water molecules due to the presence of (CH3CH2)3 N+,
which is able to form hydrogen bonding. Furthermore, the
intensity of this peak increases with the degree of functiona-
lization.44 Conversely, quaternized polymer does not show
the aforementioned peak at 757 cm
1 when TEA is incor-
porated, since a non-selective substitution of the ammo-
nium groups replaces the Cl.
TGA and DTG were performed to study the thermal sta-
bility of the ionomer. Figure 3 shows that the PSf has only
one decomposition step (≈557 C) due to the decomposition
of the skeleton chain of the polymer. PSf-Cl shows two
decomposition steps, (i) at 340 C attributed to the desorp-
tion of the chloromethyl groups, and (ii) at 510 C similar to
the decomposition of the skeleton chain of the bare PSf,
shifted to lower temperature values. For PSf-N, three
decomposition steps were observed, (i) at 185 C in both
functionalization degrees (with a weight loss of 10% and
14.9% for PSf-60-N and PSf-130-N, respectively) correspond-
ing to desorption of ammonium groups as reported by
Zhang,45 (ii) at 300 C, related to the decomposition of the
non-substituted chloromethyl groups and (iii) at 500 C,
related to the decomposition of the main skeleton of poly-
mer, respectively. It should be noted here that the percent-
age of weight loss of the PSf-N corresponds to the % w/w of
groups present in the polymer chain which is consistent
with relationships of the degree of functionalization.
Water Uptake (WU) and ionic exchange capacity
(IEC) are the other relevant parameters related to the


SALAZAR-GASTELUM ET AL. 7 of 11

TABLE 1 Different parameters of the synthesized PSf-N

Polymer Water uptake (%) IEC (meq g
1) σ (mS cm
1) Surface area (m2 g
1)
PSf ≈0 ≈0 ≈0 16.09
PSf-60-N 7.85 0.2889 0.74 23.84
PSf-130-N 23.13 0.4568 2.45 65.20

F I G U R E 4 EDX mapping for S and

N for the modified PSf-60-N and PSf-
130-N [Color figure can be viewed at
wileyonlinelibrary.com]

F I G U R E 5 Polarization curves for (a) ORR in 0.1 M NaOH saturated with O2, the scan rate of 5 mV s
1 at 1600 RPM. (b) HOR in 0.1 M
NaOH saturated with H2, the scan rate of 10 mV s
1 at 1600 RPM. [Color figure can be viewed at wileyonlinelibrary.com]

ionomers' performance since those values determine the Table 1 shows the results of different PSf materials. It
TPB composition. Water uptake (WU) was estimated is evident that the WU increased with the functionaliza-
using Equation (9): tion degree of PSf-N which suggests a more hydrophilic
structure for the PSf-130-N polymer. The hydrophilic
W wet
W dry structure observed for the polymer is consistent with the
WU ¼  100 ð9Þ
W dry amine groups attached to the polymer chain being the
group responsible for water molecules attraction. This
where Wwet and Wdry are the weights of swollen and property is very important because the ionic conductivity
dried polymers, respectively. is influenced by the water content of the ionomer used in
8 of 11

SALAZAR-GASTELUM ET AL.

F I G U R E 6 Koutecky-Levich plot (a, c, and e) for ORR and (b, d, and f) for HOR. The respective Tafel slope plots are inset in the figures
[Color figure can be viewed at wileyonlinelibrary.com]

the AEMFC. However, extremely high WU values could determination, a piece of weighed film was immersed in a
lead to an accumulation of water molecules, hindering the 0.1 M HCl solution (15 ml) at room temperature for 24 h
active sites of the catalyst which is an undesirable aspect with occasional stirring and the solution after the film was
that reduces the performance of these devices. For IEC removed was titrated to neutralization point with a 0.1 M


SALAZAR-GASTELUM ET AL.
T A B L E 2 Thermodynamics and
Ionomer E1/2 (V)
kinetics parameters of the ionomers for
ORR and HOR Oxygen reduction reaction (ORR)
Aemion® 0.66
PSf-60-N 0.73
PSf-130-N 0.70
Hydrogen oxidation reaction (HOR)
Aemion® 0.11
PSf-60-N 0.06
PSf-130-N 0.156
NaOH solution. The IEC value was estimated accordingly
Equation (10):
CHCl V HCl
CNaOH V NaOH
IEC ¼ ð10Þ
W dry
where CHCl*VHCl is the moles of HCl before titration and
CNaOH*VNaOH is the moles of the titrant, respectively, and
Wdry is the mass of the dry polymer.
Table 1 shows that by increasing the functionalization
degree in PSf-N the IEC value also increases. The pres-
ence of high quaternary ammonium groups in PSf-130-N
tends to interact with OH
during the ion exchange pro-
cess, causing an increase in functionalization. Similarly,
anionic conductivity values show that an increase in the
functionalization degree contributes to an increase over
OH
conductivity. Those properties dictate the expected
behavior during the transfer of ions and electrical charges
at the interface of the catalytic film and the surface of the
collecting electrode. It is desirable to have an increased
surface area of the materials since an increased surface
area enhances the availability of active sites on the sur-
face and it is expected that the number of active sites
increases for higher values of surface area. It is important
to point out that the surface area increased with an
observed increase in functionalization degree. Although
this analysis was performed for the polymers in the form
of solid (powder), different from its intended application
as ionomer, it is expected that the ratio of the surface
area/active sites is proportionally maintained.
The SEM–EDX analysis was performed at mapping
mode (scanned area 20 μm  20 μm) and micrographs are
shown in Figure 4. The images show the elemental analy-
sis for sulfur and nitrogen. Sulfur is a constituent element
of PSf and nitrogen is an element of the substituent groups
incorporated into the backbone of polymer structure.
From this analysis, it was possible to establish the N/S
ratio as an indicator of the amount of N atoms incorpo-
rated in both PSf-60-N and PSf-130-N materials. These
relationships are consistent with the functionalization
9 of 11
Jlim (mA cm
2) Jk (mA cm
2) Tafel slope (mV dec
1)

3.81 6.77 114.1

4.25 8.53 126.3

7.13 17.18 100.6
1.90 6.77 118.2
2.57 6.86 129.4
3.70 9.27 122.4
degree, reaching a higher value for PSf-130-N (5.6 atom.
%/atom.%) than PSf-60-N (4.03 atom.%/atom.%).
3.2 | ORR and HOR catalytic activity
The discussion of the catalytic activity on electrochemical
process is usually referenced to the potential (which is
related to the activation energy) and the current density
(related to kinetic rate of the reaction). In order to com-
pare the effect of functionalization degree in the catalytic
activity for ORR and HOR, the ionomers based on PSf-
60-N and PSf-130-N were evaluated. Figure 5a shows that
the catalytic ink prepared with the ionomer based on PSf-
130-N exhibited higher limiting current density (Jlim)
than the catalyst ink prepared with PSf-60-N in the ORR
which is related to higher anionic conductivity of the PSf-
130-N due to the presence of ammonium quaternized
groups. Similarly, PSf-130-N also exhibited higher Jlim
than PSf-60-N for the HOR (Figure 5b). However, a slight
shift of about 35 mV for ORR and 100 mV for HOR was
observed in the half wave potential (E1/2) of both reac-
tions and the E1/2 displacements could be attributed to a
polarization effect for both reactions, which is undesir-
able in fuel cell and electrolyzer applications, is impor-
tant to point out that the E1/2 take place in the mixed
region of the polarization curve at ORR and HOR, at this
region, the mass transport phenomena and the kinetics
control simultaneously the overall process, this implies
that the polarization contribution is unknown if is due to
activation energy or concentration of the species. For
comparison, a catalytic ink based on Aemion® as an
ionomer was also evaluated, demonstrating that PSf-N
based ionomers exhibited better performance than the
commercial ionomer. This enhanced performance is
attributed to physicochemical features such as IEC,
anionic conductivity, functionalization degree, etc.
Regarding ORR and HOR mechanism, Figure 6a,b
exhibited a close adjustment to the Koutecky-Levich plot
for the ORR and HOR indicating a limiting mass process
10 of 11
in both reactions, the K-L slope trend indicates that PSf-
based ionomers (PSf-60 and PSf-130) allows a higher
number of electrons transferred per molecule of either
oxygen or hydrogen in ORR and HOR, respectively.
Besides, Jk is estimated from the intercept, where this
value is related to the kinetic rate constant.
On the other hand, the Tafel plots are inset in their
respective K-L plots for each ionomer in both reactions,
where is observed Tafel slope values close to 120 mV dec
1
for ORR and HOR, respectively, which indicates a similar
RDS in each reaction. The Tafel slope value of 120 mV dec
1
for ORR in alkaline media is associated with a process where
the RDS is the first discharge step with the consumption of
MOOH with high coverage of MOO
species in the Pt sites.
On the other hand, a Tafel slope value of 120 mV dec
1 for
HOR indicates a high coverage of hydrogen on Pt sites and
indicates that the Heyrovsky step is predominantly the
RDS.46
Table 2 shows the thermodynamics parameters of the
ionomers evaluated, where is stated that PSf-130-N iono-
mer showed the highest Jlim and Jk, which is related to
kinetic rate constant at ORR and HOR. Regarding E1/2,
the based-PSf ionomers exhibited lower activation energy
and Tafel slope values similar to the reported in
literature.
4 | C ON C L U S I ON S
It is evident that the degree of functionalization of
polysulfone plays an important role in the transport of
OH
ions which is because there is a higher quantity
of quaternary ammonium groups confirmed by all the
characterizations techniques. In addition, TGA analysis
showed a decomposition step at approximately 180 C
due to the decomposition of ammonium groups
attached to the backbone of PSf and this weight loss
resulted in a higher functionalization degree. On the
other hand, the catalytic activity for ORR and HOR
exhibited better performance with the ionomers
synthesized in this study when compared to the com-
mercial Aemion®. Also, the synthesized PSf-N ionomer
possessed enhanced kinetic and thermodynamic
parameters associated with higher anionic conductivity,
higher current density, and lower activation energy. The
results suggest that PSf-N synthesized materials could be a
potential ionomer for catalytic inks of AEMFC when com-
pared to Aemion®.
A U T H O R C ON T R I B U T I O NS
Luis J. Salazar-Gastélum: Data curation (equal);
investigation (supporting); methodology (equal); vali-
dation (supporting). Mara Beltra
n-Gastélum: Data


SALAZAR-GASTELUM ET AL.
curation (supporting); formal analysis (supporting);
methodology (supporting); validation (supporting). Julio
C. Calva-Yañez: Data curation (equal); formal analysis
(equal); investigation (supporting); validation
(supporting). Shui Wai Lin: Conceptualization
(equal); investigation (equal); visualization (equal);
writing—review and editing (supporting). Daniel
Ch
avez-Velasco: Formal analysis (supporting); meth-
odology (supporting); validation (supporting). Moisés
I. Salazar-Gastélum: Data curation (equal); formal
analysis (equal); investigation (equal); validation
(equal); writing—original draft (lead); writing—review and
editing (equal). Sergio Pérez-Sicairos: Conceptualization
(equal); data curation (supporting); formal analysis (sup-
porting); funding acquisition (lead); methodology (equal);
project administration (lead); supervision (equal); writing—
review and editing (equal).
ACKNOWLEDGMENTS
The authors acknowledge to Tecnolo
gico Nacional de Méx-
ico/Instituto Tecnol

ogico de Tijuana (Grants No. 11377.21-P,
11326.21-P, and 14234.22-P) for providing material and
equipment. We thank CONACyT for ITT NMR facilities
(Grant INFR-2011-3-173395). Also, Salazar-Gastélum
L.J. thanks to Consejo Nacional de Ciencia y Tecnología
(CONACyT, Mexico) for the scholar fellowship for the Ph.D.
studies (#786162). Special thanks to Ph.D. Samgopiraj Velraj
for his comments to improve the manuscript.
DA TA AVAI LA BI LI TY S T ATE ME NT
The data that support the findings of this study are avail-
able from the corresponding author upon reasonable
request.
ORCID
Luis J. Salazar-Gastélum https://orcid.org/0000-0002-
5974-3234
Mara Beltr
an-Gastélum https://orcid.org/0000-0002-
3289-0664
Julio C. Calva-Yañez https://orcid.org/0000-0001-8032-
5988
Sergio Pérez-Sicairos https://orcid.org/0000-0002-1244-
3015
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How to cite this article: L. J. Salazar-Gastélum,
M. Beltr
an-Gastélum, J. C. Calva-Yañez, S. W. Lin,
D. Ch
avez-Velasco, M. I. Salazar-Gastélum,
S. Pérez-Sicairos, J. Appl. Polym. Sci. 2023, 140(4),
e53359. https://doi.org/10.1002/app.53359