International Journal of Advanced Engineering Research

and Science (IJAERS)

Peer-Reviewed Journal
ISSN: 2349-6495(P) | 2456-1908(O)
Vol-9, Issue-9; Sep, 2022
Journal Home Page Available: https://ijaers.com/
Article DOI: https://dx.doi.org/10.22161/ijaers.99.17

Hydrogen production by water electrolysis using TEA.PS-

BF4 ionic liquid and alternative electrocatalysts
Márcia R. Becker1, Sergio A. Arguello2, Janine C. Padilha3

Latin American Institute of Life and Nature Sciences - Federal University of Latin American Integration, Brazil
Email: [email protected]; [email protected]; [email protected]

Received: 11 Aug 2022, Abstract— Studies on water electrolysis are in permanent development to
Received in revised form: 05 Sep 2022, improve its processes with electrodes and electrolytes that offer lower
overpotential values. This work uses an ionic liquid (IL) –
Accepted: 09 Sep 2022,
tetrafluoroborate of 3-triethylammonium-propane sulfonic acid (TEA-
Available online: 14 Sep 2022 PS.BF4) – as electrolyte and studies the effect of different electroactive
©2022 The Author(s). Published by AI cathode materials on hydrogen production, such as platinum (Pt), nickel
Publication. This is an open access article (Ni), palladium (Pd), gold (Au) or silver (Ag). Water electrolysis was
under the CC BY license performed in a Hoffman Cell and analysed by chronoamperometry (CA)
(https://creativecommons.org/licenses/by/4.0/). and linear sweep voltammetry (LSV) techniques. For the electrodes
studied here, in a 0.1 M TEA-PS.BF4 solution, current density (j) values
Keywords— Electrode, electrolyte, hydrogen,
were 252-404 mA cm-2; for 0.3 M TEA-PS.BF4, values were 406-728 mA
ionic liquid, water electrolysis.
cm-2; and for 0.7 M, values were 822-1055 mA cm-2. Low activation
energy (Ea) of 5 kJ mol-1 was found for the Au cathode, 9 kJ mol-1 for Pt
and Ag, and 24 kJ mol-1 for Ni and Pd. Results show that the Ni electrode
is an attractive alternative for hydrogen production by water electrolysis
and using IL as electrolyte.

I. INTRODUCTION Water electrolysis is an electrochemical process

Hydrogen and fuel cells are considered important determined by the circulation of an electric current through
alternatives for future sustainable energy systems in the two electrodes immersed in an electrolyte solution to break
stationary power, transportation, industrial and residential water into hydrogen and oxygen. Pure water, although
sectors. Moreover, hydrogen is used in oil refineries to little dissociated, contains ions H+ and OH− which, because
produce fuels from petroleum hydrocracking, to of electric field action, migrate toward the cathode and the
manufacture fertilizers, [1, 2] in the food industry, in the anode to form hydrogen and oxygen gases. The electricity
semiconductor manufacturing process, among others. needed for the electrolysis may come from renewable
Hydrogen is a clean energy carrier with high specific energy sources such as solar, wind, and hydroelectric
energy density [3] that is usually produced by steam installations, or excess power from existing generators to
methane reforming, coal gasification and a simple process produce hydrogen during off-peak times. Due to the low
such as water electrolysis. The latter process yields high- electrical conductivity of pure water, electrolysis should be
purity, carbon dioxide-free hydrogen from renewable carried out in the presence of suitable dissolved
sources. [4, 5] Hydrogen produced by water electrolysis electrolytes to increase the conductivity of the solution.
combined with other energy generation processes may be a The electrolytes to be added to water may be acids, bases,
solution to convert long-stored chemical energy back into or salts. The reaction and standard equilibrium electrode
electricity. potential (Eo) at 298 K can be written as follows:

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Becker et al. International Journal of Advanced Engineering Research and Science, 9(9)-2022

In acid electrolyte At present, several studies are being conducted on

Cathode (-) 2H + 2e- → H2
+ o
E c = 0.00 V economically viable hydrogen production by water
electrolysis, which means finding new materials that can
Anode (+) H2O → 2H+ + ½ O2 + 2e- Eoa = +1.23 V
be used as electrodes and electrolytes. This work presents
Overall reaction is water electrolysis performance using five different
H2O → H2 + ½ O2 Eo = -1.23 V electrodes – Pt, Ni, Pd, Au and Ag – and using TEA-
PS.BF4 ionic liquid solutions as electrolytes.
In conventional water electrolysis, corrosive
electrolytes such as NaOH, KOH and H2SO4 are usually
used as conductive materials. Metal electrodes used as II. METHOD
catalysts and even the electrolyser may suffer serious
2.1. Preparation of TEA-PS.BF4
damage in these corrosive electrolytes and lose catalytic
activity. Ionic liquids (ILs) are low-melting salts that melt TEA-PS and TEA-PS∙BF4 were prepared using
at or below 273 K, which are usually composed of a large procedures available in the literature. [9] In a reaction
asymmetric organic cation and an inorganic or organic flask, 51.4 g of 1,3-propanesultone and 42.5 g of
anion. [6] ILs are materials with many interesting triethylamine were mixed with 20 mL of ethyl acetate. The
properties that may include low vapor pressure, wide reaction was stirred at 323 K for 2 h and filtered,
electrochemistry window, solubility in a wide range of producing a white solid. The precipitate was dried at 373
organic solvents and water, high conductivity, and thermal K for 2 h, producing 3-triethylammonium-propane
and chemical stability. [7] Because of these characteristics, sultonate (TEA-PS) as a white powder.
ILs can be used as electrolytes in the electrolysis of water. TEA-PS.BF4 was prepared by reacting 56.7 g of TEA-
[8] Fiegenbaum et al [9] used tetrafluoroborate of 3- PS dissolved in 5 mL of water and 33.8 mL of
triethylammonium-propane sulfonic acid (TEA-PS.BF4) in tetrafluoroboric acid at room temperature. After 2 h at 363
different concentrations as a conductive electrolyte to K, the water was removed under reduced pressure,
produce hydrogen by water electrolysis. A system using producing 75.9 g of tetrafluoroborate of the 3-
TEA-PS.BF4 in an electrochemical cell with platinum triethylammonium-propane sulfonic acid (TEA-PS.BF4) as
electrodes had current densities up to 1.77 A cm -2, and the a white viscous liquid. [1H NMR (300 MHz, DMSO,
activation energy observed was 9.3 kJ mol-1 – a low value ppm): d 1.17 (t, 3H), 1.88 (m, 2H), 3.22 (m, 2H), 3.32 (m,
that can be explained by the facilitation of proton transport 2H), 4.23 (s, 1H)].
in the organized aqueous ionic liquid media. The high 2.2. Electrochemical measurements
efficiency of this system was discussed by considering the
The conductivity (σ) of the IL solutions was measured
high conductivities associated with the Brönsted and
using an MCA 150 conductivity meter calibrated with
Lewis acidity characteristics of the IL.
standard aqueous potassium chloride solutions (491 ± 2.5
The water electrolysis process is continually subject to mg L-1 and 1000 ± 10 μS cm-1, 298 K). The
improvement, including, among other features, the use of electrochemical experiments used a Hoffmann’s Cell with
new and better electrocatalytic materials, which reduce a three-electrode arrangement (Fig. 1), composed of a
overpotential. [10] The cathodic material that is most platinum counter electrode, a platinum wire as the quasi-
active for hydrogen production by water electrolysis is reference electrode and five types of working electrodes:
platinum, but high price and limited availability are platinum (Pt), gold (Au), silver (Ag), palladium (Pd) and
limiting factors for its extensive use. Several materials nickel (Ni) – all the metal electrodes with 99.9% of purity.
have been used to make electrodes, with different effective Electrolysis was performed with 0.1 M, 0.3 M and 0.7 M
active areas, catalytic activity, electrical resistance, TEA-PS.BF4 aqueous solution. Chronoamperometry (CA)
corrosion resistivity and average lifetime. Lima et al [11] was performed in a 100 mL Hoffmann’s Cell at room
investigated vitreous carbon and pyrolytic carbon covered temperature at potentials from -1.3 to -2.0 V continuously
by nickel particles as cathodes in an aqueous solution of over 60 min to evaluate the electrodes’ stability and H2
tetrafluoroborate of the 3-triethylammonium-propane production. The residence time of the bubbles on the
sulfonic acid (TEA-PS.BF4) ionic liquid for hydrogen surface of the electrode was estimated between 15 and 30
production. They observed current density values for the min and consists of the average time between two peaks of
pyrolytic carbon cathode that were higher than those found maximum current. Linear-sweep voltammetry (LSV)
for the vitreous carbon cathode, indicating that adsorption measurements were performed in a 30 mL Hoffman’s Cell
of H+ and desorption of H2 were favoured in the former. from -2.0 to 0.0 V at a scan rate of 10 mV s-1 and range
temperature from 288 to 353 K (± 0.1 K). LSV reports the

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Becker et al. International Journal of Advanced Engineering Research and Science, 9(9)-2022

steady-state current densities dependence on a variety of

overpotential, obtained from Tafel plots according to (1): 120

Specific conductivity/mScm-1
(1) 100

where b (V dec-1) is the Tafel coefficient, which indicates 80

the rate of change in current density, j (mA cm -2), with the
applied overpotential, η (V). CA and LSV were performed 60

with an AUTOLAB model PGSTAT302N and its 40

associated NOVA software to control the experiments and
20
data acquisition.
0
0.000 0.004 0.008 0.012 0.016
IL mole fraction
Fig. 2. TEA-PS.BF4 molar fraction dependence on specific
conductivity.
The rate of the electrode reaction, characterized by
current density, depends on the nature of the electrode
surfaces and on the composition of the electrolytic solution
adjacent to the electrodes. The ions that are close to the
electrodes in the solution and therefore under the effect of
electrode form double layers, and the rate of the reaction
Fig 1. Hoffmann’s Cell used for water electrolysis.
depends on electrode potential characterized by the
reaction’s overpotential. The mechanism of the hydrogen
III. RESULTS AND DISCUSSION evolution reaction is widely accepted [12] to be a step
involving the formation of adsorbed hydrogen
The nature of electrolytes and electrodes influences the
electrolysis process. TEA-PS.BF4 had its conductivities in H+ + e- → Hads (R1)
aqueous solutions measured, and the results are shown in which is followed by either chemical desorption
Fig. 2. Specific conductivity values increased with higher
2Hads → H2 (R2)
IL concentration, which may be attributed to its higher
dissociation degree in water. At these concentrations – 0.1 or electrochemical desorption
M, 0.3 M and 0.7 M – water is in the TEA-PS.BF4 H+ + e- + Hads → H2 (R3)
network, breaking the strong Coulombic interactions, where the subscript ads represent the adsorbed status.
resulting in solvation and increase in the dissociation of Increasing overpotential could lead to a change in the
the TEA-PS+ and BF4- ions. In this concentration range, mechanism rate. The rate-determining step will change at
the electric force attributed to the presence of the ions different potential ranges. When the potential is low,
dissociated and subjected to the electric field seems to electron transfer (R1) is not as fast as desorption and
prevail over the frictional forces attributed to the increase hydrogen adsorption will be the rate-determining step. On
in the viscosity of the medium due to IL concentration. the other hand, when the potential is high enough for the
This indicates that ionic conductivity is not only related to hydrogen adsorption rate to be higher than the desorption
the viscosity but also to the ion-ion, ion-solvent, and rate, hydrogen desorption will be the rate-determining step
solvent-solvent interactions. (R2 and R3). Fig. 3 shows increasing current density
values with increasing potential for the electrodes tested,
indicating that larger electric power is consumed by the
electrolyser and therefore hydrogen production is higher.
Pt with the IL presented the best performance at any
potential range. Its current density increases from 200 to
400 mA cm-2. Similarly, Ni presented variation of 130 to
350 mA cm-2. Pd and Au, with small differences especially
at lower potentials, presented behaviour similar to Ni. Ag
presents the smallest current density variation, being
subject to low or high overpotentials. Its variation was

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Becker et al. International Journal of Advanced Engineering Research and Science, 9(9)-2022

only 140-250 mA cm-2, showing that working at smaller electrodes. This may contribute to their poor performance
overpotentials (-1.3 V) may be more advantageous for Ag. in electrolysis compared to other electrodes.
Table 1: Release time of the H2 bubbles on the electrodes
surface.
Release time (min)
-1.3 V -1.5 V -1.7 V -2.0 V
Pt 2±1 1.2 ± 0.6 1.0 ± 0.4 0.6 ± 0.2
Ag 4±1 0.9 ± 0.5 1.2 ± 0.6 3.0 ± 2
Au 1.2 ± 0.6 1.4 ± 0.8 1.2 ± 0.2 1.4 ± 0.7
Ni 1.6 ± 0.6 2.2 ± 0.9 1.0 ± 0.5 2±2
Pd 3±2 1.1 ± 0.6 1.2 ± 0.6 1.0 ± 0.4
Fig 3. Potential effect on the current density for 0.1 M
TEA-PS.BF4 solution. Fig. 5 shows the influence of TEA-PS.BF4 concentration
on current density at different potentials and with different
electrodes. The results show an increase in current density
In addition to the overpotential imposed on the system,
values with increasing concentration of the IL. This
which is known to favour electrolysis, the system is
behaviour agrees with those found in conductivity
affected by bubble formation on the work electrode’s
measurements where conductivity increases with higher
surface. The hydrogen bubbles produced tend to
concentration of the LI solution. The results also indicate
electrically insulate the active sites in the electrode surface,
strong dependence of water electrolysis on the electrode’s
reducing its activity and consequently the current densities
material.
values. Fig. 4 and Table 1 show longer release time for
bubbles produced at higher potential (-1.3 V) (Fig. 4a) The data on Ni electrode showed efficiency only 10%
than at lower potential (-2.0 V) (Fig. 4b). When several lower than Pt, indicating Ni as a promising material to be
bubbles, represented by the circles, are produced, they used as a catalyst in water electrolysis with TEA-PS.BF4.
adhered to the electrode, which remains with its active area In addition, systems using Pd, Au and especially Ag
unavailable for the reactions, and current values decrease. appear to be strongly influenced by the concentration of
As soon as the bubbles are released, the reaction resumes the IL, at least more than those using Pt and Ni. Electrodes
and current increase again. Systems with higher amounts made of Pt, Ni, Pd, Au and Ag were stable during the
of bubbles tend to leave the electrode less exposed; electrolysis process.
therefore, those with higher potentials are privileged and
present better performances. [13]

(a) (b)
Fig. 4. Bubble release time to (a) -1.3 V or to (b) -2.0 V on
Fig. 5. Effect of TEA-PS.BF4 concentration on current
Pt electrode with 0.1 M TEA-PS.BF4 solution.
density at -2.0 V and 298 K.

Interestingly, for the systems proposed here, the time

Kinetic parameters for hydrogen production were
during which the bubbles remain on the surface of the
evaluated by exchange current density at the open‐circuit
electrodes does not seem to vary significantly within the
potential (jo) and cathodic slope (bc); both are shown in
range of potentials studied. However, it can be inferred
Table 2. Hydrogen production on the electrode is given by
that on the Ag surface, the bubbles remain longer at -1.3
the slopes and intercept at E = Eeq by plotting ln|j| versus
and -2.0 V potentials than on the surface of the other
E.

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Becker et al. International Journal of Advanced Engineering Research and Science, 9(9)-2022

Table 2. Tafel parameters of the HER to different cathodes Fig. 7. Temperature effect on the current density for the
and TEA-PS.BF4 solutions. system using 0.1 M TEA-PS.BF4 at -2.0 V with Pt (∎), Ni
(•), Pd (◆), Au () and Ag ().
jo (µA cm-2) bc (mV dec-1) Eeq (V)
0.1 M 0.3 M 0.7 M 0.1 M 0.3 M 0.7 M 0.1 M 0.3 M 0.7 M
Pt 1.2 2.8 6.5 104 97 83 0.70 -0.11 -0.20
Linear increase of the density current with temperature
Ni 5.2 3.0 0.8 120 106 79 -0.20 -0.09 -0.06 can be observed for all cathodes and between 298 and 318
Pd 367 320 324 61 110 116 -0.35 -0.55 -0.26 K. Table 3 reports Ea values for each cathode studied. The
Au 4.9 3.6 3.6 63 125 44 -0.35 -0.21 -0.03 adjusted R-square is shown to demonstrate the good
Ag 1.2 2.5 5.1 96 66 6 -0.20 -0.04 0.28 approximation of the Arrhenius plots.
Table 3. Activation energy for the system with 0.1 M TEA-
It is worth noting that the highest exchange current PS.BF4 solution.
density (jo) values were observed for Pd. Pt and Ag show Cathode Ea/kJ mol-1 R2
increase in current density with increasing IL
concentration. Ni and Au, in turn, present lower jo with Platinum 9 0.94
higher IL concentration. The lowest cathodic slope was Nickel 24 0.94
observed for Ag with 0.7 M TEA-PS.BF4 solution, Gold 5 0.96
followed by Au at the same concentration and Pd with 0.1
M solution. For Ag electrocatalyst, lower electrode Silver 9 0.98
polarization is needed for proton adsorption/desorption, Palladium 25 0.96
and the reaction occurs faster (kinetic factor). It indicates Ea values are low for all electrodes, and Au, Ag and Pt
that IL concentration influences electrode activity, and the have good performances and are promising materials to be
best solution seems to be 0.7 M TEA-PS.BF4 with Au, Ag, used as working electrodes in water electrolysis with this
Ni and 0.1 M TEA-PS.BF4 with Au and Pd. IL. However, Ea values were higher for nickel and
Electrodes’ catalytic performance was measured by palladium than for those materials previously mentioned.
activation energies (Ea) for the HER. Arrhenius-type Increase in temperature in the system may lead to higher
dependence predicts that the exponential increases with the density and diameter of the bubbles adsorbed on their
reciprocal of the temperature, which, in a logarithmic surface. This increase in the surface area covered reduces
form, is as (2): the electrocatalytic area and therefore current density. This
lnj = lnA -Ea ⁄ RT (2) behaviour seems to be linear with increasing temperature
but is more pronounced for Ni and Pd, making the slope of
Where A is the pre-exponential factor (cm s-1), Ea is the
the line smaller. These values are comparable to those
activation energy, R is the universal gas constant (8.31 J
found in the literature when the electrolyte used is 30%
K−1 mol−1), and T (K) is the absolute temperature.
KOH solution, that is, 16 kJ mol-1. [9]
The effect of temperature on the system with 0.1 M
TEA-PS.BF4 solution at 288-353 K with applied potential
of -2.0 V is shown in Fig. 7. IV. CONCLUSIONS
Water electrolysis was performed with Pt, Ni, Pd, Au or
Ag electrodes using TEA-PS.BF4 as electrolyte. The Ni
electrode’s efficiency was only 10% lower than Pt,
pointing to it as a promising material to be used use as a
catalyst in water electrolysis. Pt, Ni, Pd, Au and Ag
electrodes were stable during the electrolysis process.
The best IL/cathode combination was obtained at 0.7 M
TEA-PS.BF4 for Au, Ag, Ni and at 0.1 M TEA-PS.BF4 for
Au and Pd, with high hydrogen production.
The major point of these studies is the economical
attractiveness of performing water electrolysis using an
inexpensive electrode such as Ni and a very stable IL. The
system constituted by these elements must be considered

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Becker et al. International Journal of Advanced Engineering Research and Science, 9(9)-2022

as an alternative to the currently employed to produce [10] Fiegenbaum, F., Souza, M. O., Becker, M. R., Martini, E.
high-purity hydrogen through electrolysis. M., Souza, R. F. (2015). Electrocatalytic activities of
cathode electrodes for water electrolysis using tetra-alkyl-
ammonium-sulfonic acid ionic liquid as electrolyte. Journal
ACKNOWLEDGEMENTS of Power Sources, 280, 12-17.
https://doi.org/10.1016/j.jpowsour.2015.01.082
Thanks to University of the Latin-American Integration
[11] Lima D. W., Trombetta, F., Benvenutti, P. P., Teixeira, S.
(UNILA), Graduate Support Program (PROAP) and Itaipu R., Martini, E. M. A. (2019) Effect of different carbon
Technological Park Foundation/Araucaria Foundation supports for Ni particles for the HER in
(FPTI/FA) by the financial support, to Hydrogen Research tetra‐alkylammonium‐sulfonic acid media. Int J Energy Res.
Center (NUPHI) and to Federal University of Rio Grande 1–12. https://doi.org/10.1002/er.4765
do Sul (UFRGS). [12] Zeng, K. & Zhang, D. (2010) Recent progress in alkaline
water electrolysis for hydrogen production and applications.
Progress in Energy and Combustion Science, 36, 307-326.
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