Hydrogen Production by Water Electrolysis - A Review

Results in Engineering 20 (2023) 101426
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Hydrogen production by water electrolysis technologies: A review

Mostafa El-Shafie
Institutes of Innovation for Future Society, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8601, Japan
A R T I C L E I N F O A B S T R A C T
Keywords: Hydrogen as an energy source has been identified as an optimal pathway for mitigating climate change by
Proton exchange membrane combining renewable electricity with water electrolysis systems. Proton exchange membrane (PEM) technology
Hydrogen production has received a substantial amount of attention because of its ability to efficiently produce high-purity hydrogen
Impure water
while minimising challenges associated with handling and maintenance. Another hydrogen generation tech
Membrane electrode assembly
Water electrolysis
nology, alkaline water electrolysis (AWE), has been widely used in commercial hydrogen production applica
Renewable energy tions. Anion exchange membrane (AEM) technology can produce hydrogen at relatively low costs because the
noble metal catalysts used in PEM and AWE systems are replaced with conventional low-cost electrocatalysts.
Solid oxide electrolyzer cell (SOEC) technology is another electrolysis technology for producing hydrogen at
relatively high conversion efficiencies, low cost, and with low associated emissions. However, the operating
temperatures of SOECs are high which necessitates long startup times. This review addresses the current state of
technologies capable of using impure water in water electrolysis systems. Commercially available water elec
trolysis systems were extensively discussed and compared. The technical barriers of hydrogen production by PEM
and AEM were also investigated. Furthermore, commercial PEM stack electrolyzer performance was evaluated
using artificial river water (soft water). An integrated system approach was recommended for meeting the power
and pure water demands using reversible seawater by combining renewable electricity, water electrolysis, and
fuel cells. AEM performance was considered to be low, requiring further developments to enhance the mem
brane’s lifetime.
1. Introduction approximately 96% of the global market [6]. Carbon dioxide (CO2)
emissions into the atmosphere contribute substantially to the green
In recent years, concerns about the unsustainable use of fossil fuels house gas (GHG) effect, which is the key driver in climate change [66,
and global warming have grown due to increases in global energy de 68,69]. Several major international meetings have been held to address
mand as a result of continuous population growth and energy-intensive global warming, including COP 26 (Glasgow-UK, 2021) and COP 27
lifestyles. Energy resources are needed to support all human activities (Sharm El-Sheikh-Egypt, 2022). The world’s governments are joining
[1–3]. Therefore, the development of renewable energy sources has forces to confront climate change by transitioning to carbon-free fuels.
essential in the acceleration of the energy transition toward global The international energy agency (IEA) proposed targets for the primary
carbon neutrality. Hydrogen (H2) is considered one of the most energy sources of hydrogen production from 2020 to 2050 to achieve net
carbon-free energy carriers, as only water is produced when it reacts zero emissions, as shown in Figure (1) [70]. Fossil fuels (without carbon
with oxygen to generate electricity [4]. In addition, hydrogen has capture) as sources of hydrogen are not sustainable and do not
beneficial physical and chemical properties as a clean energy carrier contribute to net zero emissions.
such as its high gravimetric energy density (140 MJ/kg) [5] (see CO2 and other GHG emissions must be avoided in the hydrogen
Tables 1–7). production processes. Today, most of the hydrogen produced globally is
For several decades, various hydrogen production technologies have generated by steam methane reforming and water electrolysis processes.
been investigated, such as steam methane reforming, biomass, water The global demand for hydrogen in 2020 was 90 Mt—70 Mt of which
electrolysis, etc. [7,65–67]. Table (1) lists the shares of different was pure hydrogen generated with no carbon emissions [72]. Further
hydrogen production technologies of the total production capacity. more, most of the generated hydrogen was used in oil refining or
Currently, hydrogen production from hydrocarbons comprises petrochemical applications, fuel cells, and industrial chemicals [73,74].
E-mail address: [email protected].
https://doi.org/10.1016/j.rineng.2023.101426
Received 1 July 2023; Received in revised form 31 August 2023; Accepted 14 September 2023
Available online 19 September 2023
2590-1230/© 2023 The Author. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
M. El-Shafie Results in Engineering 20 (2023) 101426
Table 1 generating high-purity hydrogen. PEM water electrolysis technology

Global hydrogen production sources [6]. development includes improving catalyst and system performance and
Energy Source Bcm3/yra Share (%) integrating renewable energy. The fundamentals of PEM water elec
trolysis technology have been investigated [83]. Hydrogen production
Natural gas 240 48
Oil 150 30 by water electrolysis offers several advantages, including high-purity
Coal 90 18 H2, no output pollutants, and a wide range of input energy sources. In
Electrolysis 20 4 addition, H2 production from water electrolysis has been used for many
Total 500 100 years in industrial applications [71].
a
Bcm: billion cubic meters. The costs of green hydrogen production are influenced by the
renewable electricity generated from solar, tidal, geothermal and wind
Most of the hydrogen has been generated from steam methane reform energy [71]. Moreover, solar photovoltaic (PV) has become the
ing. Hydrogen can be generated from renewable energy sources such as lowest-cost source of green electricity. An innovative cooling system for
solar or wind energy or non-renewable energy such as fossil fuels, a PV solar unit comprised of a thermoelectric layer utilizing hybrid
particularly methane reforming. nanomaterial has been investigated [84,85]. It has been shown that the
In addition, the integration of nuclear energy as a source of elec optimal locations for solar energy are the in the Middle East. Further
tricity for hydrogen production plants has been recently investigated more, hydrogen production processes involving electrolysis can operate
[75]. Hydrogen can be generated from water using different technolo flexibly using various renewable electricity sources. The most significant
gies, including water electrolysis and splitting, the latter of which can be factor is the stability of the renewable electricity source. Figure (2) il
achieved through thermochemical processes, biomass conversion, or lustrates the long-term hydrogen production cost of electrolyzers in
photocatalysis [76]. The splitting of water into hydrogen and oxygen various regions worldwide using solar PV and wind energy systems [71].
occurs through a series of chemical reactions. Water conversion occurs The hydrogen-based fuels are more economical, although they have
at a high temperature range of 800–2000 ᵒC [77]. Solar and nuclear higher hydrogen production costs and less operating time at entire load
power plants can generate the required heat for the thermochemical operations than other fuels. Therefore, the green hydrogen production
water splitting process [78]. pathway is the optimal solution to reduce the environmental impacts of
The production of hydrogen by photocatalysis is a promising method GHGs. However, water electrolysis requires higher energy consumption;
in which water is dissociated into hydrogen and oxygen using solar industrial electrolyzer energy consumption is 4.5–5 kWh/m3. High en
energy and TiO2 as a photocatalyst [79]. The main disadvantages of this ergy consumption is a substantial challenge that should be addressed to
technology are the use of TiO2 which leads to a wide band gap in the minimize the hydrogen production costs. An overview of the global
visible light region, and the evolution of over potential [80]. Plasma hydrogen production trends and best practices in Saudi Arabia was
technology has also received a great deal of attention because of its presented, with national policy recommendations for the energy in
ability to dissociate gases into their elements. Hydrogen production dustry [86]. In addition, industrial-scale hydrogen production in
from water vapour by dielectric barrier discharge (DBD) plasma as well Morocco for sustainable technologies has been evaluated [87].
as hydrogen production from water containing impurities by DBD Furthermore, a study of hydrogen production in Ireland was performed
plasma have been recently investigated [81, 82]. which includes the deployment of power-to-gas (P2G) systems, the
Hydrogen is primarily generated by steam reformation of fossil fuels, transition to renewable energy systems, and industrial heating re
the process operation of which is complicated by carbon dioxide emis quirements [88].
sions. Water electrolysis is the most effective zero-emission hydrogen Water electrolysis can produce high purity hydrogen and can be
production technology when utilizing renewable energy as the elec feasibly combined with renewable energy. Water is a requirement of
tricity source. Polymer electrolyte membrane (PEM) water electrolysis these systems as the main input to the electrolyzer to produce hydrogen.
using an ion exchange membrane is a high efficiency technology for Also, water electrolysis energy consumption in conventional industrial
Table 2
Comparison of the available water electrolyzer technologies.
Specification Alkaline [48, 60] PEM [48, 60] SOEC [7] AEM [8,9]
Technology maturity Mature Commercial R&D R&D

Cell temperature, ◦ C 65–100 70–90 900–1000 50–70
Cell pressure, bar 25–30 30–80 <30 − 30
Current density, mA/cm2 200–500 800–2500 300–1000 200–500
Cell voltage, V 1.8–2.4 1.8–2.2 0.95–1.3 1.8–2.2
Voltage efficiency, % 50–70.8 48.5–65.5 81–86 39.7
Specific system energy consumption, 4.5–7.5 5.8–7.5 2.5–3.5 4.8–5.2
kWh/Nm3
Hydrogen production, Nm3/hr <760 0.265–30 – 0.25–1
Stack lifetime, hr 10, 000 <20,000 <40,000 NA
Electrolyte 20–30% KOH Perflurosulfonated acid Yttria-stabilized zirconia DVB polymer support with
(PFSA) (YSZ) KOH
or NaHCO3
Separator Asbestos, NiO, ZrO2, stabilized with PFSA (e.g., Nafion) Solid electrolyte quaternary ammonia
PPS mesh polysulfone (QAPS)
Charge carrier OH− H+ O−2 OH−
OER catalyst Ni-coated perforated stainless steel Ir/Ru oxide Perovskite-type CO3O4
HER catalyst Ni Platinum Ni/YSZ Ni
Hydrogen purity, (vol%) 99.3–99.9 99.999 – 99.99
Capital cost (€/kWel) 1000–1200 1860–2320 >2000 NA
Abbreviations.
OER: oxygen evolution reaction.
HER: hydrogen evolution reaction.
NA: not available.
2
Cathode: 2H+ + 2e− → H2 (Urev = 0.00 V) (2)

application is relatively high and about 5 kWh m− 3H2. In addition,
availability of fresh water is a serious problem in many regions of the Overall reaction: H2O → H2 + ½ O2 (Urev = 1.229 V) (3)
world. Therefore, it is important to further develop water electrolysis
technologies and minimize the energy consumption to meet the re The reversible cell voltage can be derived as a function of the Gibbs
quirements of sustainable hydrogen production. The current study aims free energy:
to present a detailed analysis and an overview of the progress of con ΔG = ΔH − Q = ΔH − TΔS (4)
ventional hydrogen electrolyzers. Thermodynamic analyses of hydrogen
production via water electrolysis types are also discussed, along with the ΔG = zFUrev (5)
technical barriers associated with using impure water in different elec
trolyzer types. Potential technology advancements and future ap ΔGR
Urev = (6)
proaches are also highlighted. Finally, hydrogen production costs and zF
challenges in the field are evaluated. The reversible voltage is determined at standard temperature and
pressure (298.15 K and 1 atm), ΔGR = 237.21 kJ/mol, ΔS = 0.1631 kJ/
2. Thermodynamic analysis of water electrolysis mol K, and ΔН = 285.84 kJ/mol. The number of electrons is z = 2, while
F is Faraday’s constant F = 96485 C/mol. By substituting ΔGR and ΔН0,
Generally, purified or deionized water can be used as the feedstock the theoretical potential value is obtained, Urev = 1.229 V [89,91].
for PEM electrolyzers. Fresh water is available from rivers, groundwater, Water electrolysis begins operation by connecting the applied voltage to
and lakes but requires several filtration steps. Furthermore, the water the cell electrodes (cathode and anode). The applied potential decreases
types can vary based on the hardness and salts in the water. Numerous due to the cell overpotential. The activation and ohmic overpotential are
experimental studies of PEM electrolyzer stacks and systems operation characterized as the cell overpotential, the cell operating voltage is the
have been performed over the last 15 years [66,89]. Renewable elec summation of the reversible, activation, ohmic overpotential [92],
tricity can provide continuous and stable electricity for hydrogen elec expressed as follows:
trolyzers. The National Renewable Energy Laboratory (NREL) in the US
demonstrated the application of storing excess wind energy as hydrogen Ucell = Urev + Uact + Uohm (7)
and later using it to charge cars and power homes with the use of fuel The proton transfer and kinetic electrochemical behaviour in the
cells [90]. Due to the importance of energy consumption in hydrogen water electrolyzer comprise the activation overpotential. Losses in the
electrolyzers, we will investigate the thermodynamics of the electro applied voltage occur during the water decomposition chemical re
chemical process in the following subsection. actions, and electrons transfer to or from the electrodes. The ohmic
overpotential is expressed as the potential losses due to the resistance of
2.1. Energy efficiency and energy consumption of water electrolysis the membrane against the electron flow, which depend on the water
electrolysis type and the membrane thickness. Therefore, the ohmic
The electrochemical decomposition process of water occurs accord overpotential can be calculated as a function of membrane conductivity,
ing to the following anode and cathode evolution reactions. The anode thickness, and current density [93]. The numerical simulation results of
and cathode reactions and their respective reversible potential in a the ohmic overpotential compared with the reversible potential of the
water electrolytic cell can be expressed as follows: electrolyzer cell are presented in Figure (3). The simulation predicted
the overpotential losses in water electrolyzers [94]. The ohmic resis
Anode: H2O →2H+ + ½ O2 + 2e− (Urev = 1.229 V) (1)
tance is also estimated as a function of the ionic and electronic
Table 3
Comparison of OER performance with various catalysts.
Catalyst Substrate Electrolyte Stability Loading η10 (mV) Tafel slope (mV dec− 1) Ref.
− 2 − 2
Ultrafine Ir NPs GC 0.5 M HClO4 1,000 cycles or 20,000s@10 mAcm 90 μgIr cm 290 65.1 [10]
Ir@HEDP/CNBs GC 0.1 M HClO4 5 h@10 mAcm− 2 – 290 49.1 [11]
Ir-SA@Fe@NCNT GC 0.5 M H2SO4 12 h@10 mAcm− 2 1.14 μgIr cm− 2 250 58.2 [12]
Ir0.06Co2.94O4 Au electrode 0.1 M HClO4 200 h@10 mAcm− 2 5 μgIr cm− 2 292 45 [13]
3D Ir GC 0.1 M HClO4 8 [email protected] mAcm− 2 11.5 μgIr cm− 2 240 40.8 [14]
Ir/g-C3N4/NG GC 0.5 M H2SO4 2,000 cycles 6.7 μgIr cm− 2 287 72.8 [15]
Mesoporous Ir nanosheets GC 0.5 M H2SO4 8 h@10 mAcm− 2 – 240 49 [16]
Amorphous Ir nanosheets GC 0.1 M HClO4 5,000 cycles 0.2 mgcm− 2 255 40 [17]
Ru–N–C GC 0.5 M H2SO4 30 [email protected] V 0.28 mgcm− 2 267 52.6 [18]
Ru1–Pt3Cu GC 0.1 M HClO4 28 h@10 mAcm− 2 1.92 μgRu cm− 2 220 – [19]
Ru/RuS2 GC 0.5 M H2SO4 3,000 cycles or 24 h@10 mAcm− 2 0.849 mgcm− 2 201 47.2 [20]
fcc-Ru octahedral GC 0.05 M H2SO4 – – 168 47.8 [21]
IrNi NPNWs GC 0.1 M HClO4 200min@5 mAcm− 2 25 μgIr cm− 2 283 56.7 [22]
Ir3Cu GC 0.1 M HClO4 12 h@5 mAcm− 2 – 298 47.4 [23]
IrNi NCs GC 0.1 M HClO4 2 h@5 mAcm− 2 12.5 μgIr cm− 2 280 – [24]
Rh22Ir78 GC 0.5 M H2SO4 2,000 cycles 9.8 μgIr cm− 2 292 101 [25]
IrRu@Te GC 0.5 M H2SO4 20 h@10 mAcm− 2 0.6 mgcm− 2 220 35 [26]
Co–RuIr Au electrode 0.1 M HClO4 25 h@10 mAcm− 2 – 235 66.9 [27]
2
Pt39Ir10Pd11 GC 0.1 M HClO4 – 16.8 μgPt + Ir + Pd cm− 372 128.7 [28]
IrNiCu DNF GC 0.1 M HClO4 2,500 cycles 20 μgIr cm− 2 300 48 [29]
Co–IrCu GC 0.1 M HClO4 2,000 cycles 20 μgIr cm− 2 290 50 [30]
IrCoNi PHNC GC 0.1 M HClO4 200min@5 mAcm− 2 10 μgIr cm− 2 303 53.8 [31]
IrOxQD/GDY GC 0.5 M H2SO4 3,000 cycles or 20 [email protected] V – 236 70 [32]
IrHfxOy GC 0.1 M HClO4 6 h@5 mAcm− 2 – 330 60 [33]
Cr0.6Ru0.4O2 GC 0.5 M H2SO4 10 h@10 mAcm− 2 – 178 58 [34]
W0.2Er0.1Ru0.7O2-δ GC 0.5 M H2SO4 500 h@10 mAcm− 2 0.33 mgcm− 2 168 66.8 [35]
a/c-RuO2 GC 0.1 M HClO4 60 h@10 mAcm− 2 0.404 mgcm− 2 205 48.6 [36]
RuIrOx GC 0.5 M H2SO4 24 h@10 mAcm− 2 10 μgIr + Ru cm− 2 233 42 [37]
3
resistances [95]. The largest overpotential of 2.6 V was obtained at the hydrogen in large-scale applications. Nickel (Ni) and cobalt oxides are
Pt electrode on the anode side, and the overpotential increased with the utilized to form the anode and cathode materials, respectively. More
current density. Moreover, the cathode overpotential was lower than over, potassium hydroxide (KOH) electrolyte is the most useable with
that of the anode because of the rapid kinetic reactions at the anode 30–40% and the alkalinity is generated by circulating the electrolyte
surface. across both electrodes [112,113]. Figure (5) shows a schematic diagram
The energy consumption of a water electrolyzer is an important of an alkaline water electrolyzer cell [114]. The anode and cathode re
parameter to evaluate the cell performance over an extended period. actions occur to produce hydrogen and oxygen. The separating porous
The theoretical decomposition cell voltage of water is 1.229 V. The diaphragm is installed between the two electrodes, and the hydroxyl
hydrogen production efficiency from the cell is about 100%. The elec ions (OH− ) are generated and passed through the porous diaphragm
trolyzer energy consumption can be determined according to the materials, which are made of ceramic oxide materials such as asbestos
following formula [96]: and polymers [115,116]. The hydrogen and hydroxide are produced at
the cathode at moderate operating temperatures of 65–100 ◦ C; oxygen is
∫Δt
then generated at the anode by the hydroxide reaction. The conversion
Ncell .Icell .Ucell dt
efficiency of alkaline water electrolyzers is 60–80%, and the cell oper
CE = 0
(8) ating voltage is 1.8–2.4 V [117]. The advantages of alkaline electro
∫Δt
lyzers are that they can operate at low temperatures and do not require
fH2 dt
catalysts to activate and produce hydrogen [118]. In contrast, alkaline
0
electrolyzer electrode corrosion is considered the foremost challenge
because of the presence of an alkali solution.
Where Ncell is the number of cells that constitute the electrolysis module,
fH2 is the hydrogen production rate in Nm3/h, and Icell and Vcell are the
3.2. Proton exchange membrane electrolyzer
cell current in A and voltage in V, respectively, determined for a given
time interval of Δt. The cell efficiency and power consumption are
PEM water electrolyzers can produce high-purity hydrogen at lower
determined at the applied current. The electrolyzer efficiency is defined
temperature ranges of 70–90 ◦ C. IrO2 and Pt are used as the anode and
as the ratio between the higher heating value (HHV) of hydrogen and the
cathode catalyst materials, respectively [119,120]. Nafion membrane is
total energy consumption (CE) in kWh/Nm3, calculated as follows [96]:
typically used to conduct the hydrogen ions (H+); it is applied as a solid
ηE =
HHV of H2
× 100 (9) electrolyte, as opposed to the liquid electrolyte in alkaline electrolyzers.
CE A PEM electrolyzer cell schematic diagram and reaction mechanism are
Industrial cell voltage is applied at a range of 1.8–2.6 V, meaning that shown in Figure (6). Hydrogen ions migrate through the solid membrane
the voltage values higher than the theoretical voltage of 1.229 V are to form hydrogen molecules. Because of the electrolyte’s acidic nature
expressed by the greater overpotential and ohmic overpotential losses. A and the electrode’s metallic surfaces, the reaction kinetics of PEM
theoretical analysis of the cell voltage versus the energy consumption electrolyzers are rapidly induced compared with those of an alkaline cell
and energy efficiency is shown in Figure (4). It can be seen that energy [121]. As a result, PEM electrolyzers are safer and can operate at at
consumption increases with increasing cell voltage. In addition, energy mospheric pressure on the anode side while the cathode side is exposed
efficiency decreases at higher cell potentials, and the higher operating to higher pressures [89, 122]. A significant challenge of PEM electro
cell voltage influences the electrolyzer performance. lyzers is their difficulty in scaling up for large-scale (MW) applications.
Therefore, an extensive analysis should be performed to validate the
large-scale unit’s characteristics and the expected lifetime of PEM
3. Water electrolysis types
electrolyzers.
Most water electrolysis technologies generate hydrogen and oxygen
3.3. Solid oxide electrolyzer
from water at lower operating temperatures [97–100]. The main types
of water electrolysis for generating hydrogen are alkaline electrolysis [8,
In solid oxide electrolyzers, the cell operates at substantially higher
101–104], PEM electrolysis [105–107], solid oxide electrolysis (SOE)
temperatures than alkaline and PEM electrolyzers in the range of
[46], and polymer anion exchange membrane (AEM) electrolysis
900–1000 ◦ C. The cell electrodes are made from nickel, and less elec
[108–111]. These electrolyzer types are discussed in the following
tricity is required for the hydrogen separation process, illustrated in
subsections.
Figure (7) [114]. Different heat input sources, such as waste heat and
nuclear energy, can be used to reduce the dependence on electricity for
3.1. Alkaline water electrolyzer heating [123,124]. In addition, the cell efficiency increases with higher
operating temperatures. Unfortunately, high temperatures also increase
Alkaline water electrolyzers are commonly used to produce the rate of electrolyte degradation and reduce the SOEC lifetime. In
Table 4
Gives the performance of AWE using fluctuating renewable power for different HER and OER catalysts [38].
Reaction Stability test protocol Catalyst Electrolyte Temperature Current density for η (mA/ ηinitial ηend Ref.
(◦C) cm2) (mV) (mV)
HER − 200 mA/cm, 1 h - OCP, 1 h: 50 cycles MnnCo1enPx 1 M KOH 25 100 105 195 [39]
− 0.4–0.5 V, 0.5 V/s, CV, 40,000 cycles Co-ns/Ni 7 M KOH – 100 68 64 [40]
− 0.25–0.4 V, 5 mV/s, LSV, 3000 scans NiFe/CP 1 M KOH RT 100 245 265 [41]
− 300 mA/cm, 30 mine 0.074 V, 60 s, 33 Raney Ni 30% KOH 70 300 277 557 [42]
cycles
OER 0.5–1.8 V, 1 V/s, CV, 60,000 cycles Co-ns/Ni 7 M KOH – 100 350 360 [40]
0.5–1.8 V, 1 V/s, CV, 20,000 cycles NiFe-HyOx/316SS 7 M KOH 20 100 267 262 [43]
0–240 mA/cm2,1 mA/s, CV, 2000 cycles Ni0.9Fe0.1Co2O4/ 1 M KOH 22 240 563 583 [44]
Ni
600 mA/cm2 for 3 se0.3 V for 3 s, 2000 NiCoOx/Ni 7 M KOH 25 100 420 600 [45]
cycles
4
addition, existing SOEC demonstrations can only operate at the kilowatt Table 6
scale. Maximum levels of cationic elements in drinking water [61].
Elements Contaminants Concentration (mg/L)
Primary Barium 2
3.4. Anion exchange membrane Chromium 0.1
Selenium 0.05
AEM is the most recent water electrolysis technology, primarily Arsenic 0.01
driven by electrochemical applications for hydrogen production over Antimony 0.006
Cadmium 0.005
the last few years. AEM electrolyzers combine the advantages of alkaline
Beryllium 0.004
and PEM water electrolyzers [125]. The reaction mechanism of an AEM Tellurium 0.002
cell is illustrated in Figure (8). As can be seen, hydrogen and hydroxyl Secondary Zinc 5
are generated at the cathode side. Copper 1.3
Moreover, non-noble catalyst materials can be used for AEM cells, Iron 0.3
Aluminum 0.2
leading to lower hydrogen production costs [47]. However, AEM per Silver 0.1
formance is still low due to the poor catalyst activity and the lower Manganese 0.05
conductivity of the AEM membrane. Therefore, AEM water electrolysis
requires further investigations, specifically regarding membrane mate
rials, cell cost, and efficiency. significant development to be utilized for industrial-scale H2 production
The most important operating conditions for the four water elec in the near term. In addition, the different water electrolysis technolo
trolyzer types are summarized in Table (2). It is clear that the SOEC and gies have different challenges, such as cell performance, durability,
the AEM electrolyzers are still at the research and development (R&D) membrane materials, catalysts, and cell cost.
stage and are less mature compared with alkaline and PEM technologies.
In addition, the benefits of AEM include lower overall cost and high H2
production stability [48]. However, AEM technology requires
Table 5
AEM water electrolysis component materials [46].
Membrane electrode assembly Operating conditions Electrolyte Ref.
Anode Cathode Membrane Ionomer
GDL Catalyst Loading GDL Catalyst Loading Voltage Current T

(mg (mg (V) density (◦ C)
cm− 2) cm− 2) (mA
cm− 2)
Ti foam IrO2 2.9 Ti foam Pt black 3.2 A-201, Tokuyama AS-4 1.8 399 50 deionized [47]
water
Ni foam Ni/ 36 Carbon CuCoO3 7.4 A-201, Tokuyama PTFE 1.9 470 50 1% [48]
CeO2–La2O3/C cloth K2CO3/
KHCO3
Carbon Pb2Ru2O6.5 2.5 Carbon Pt black 2.5 Chloromethylated PSF-TMA + 1.8 400 50 Ultra-pure [49]
paper paper PSF(CMPSF) Cl-, PSF- water
ABCO + Cl-
or PSF-1M
+ Cl-)
Ni foam Ni–Fe 40 Stainless Ni–Mo 40 (xQAPS) (xQAPS) 1.85 400 70 Ultrapure [50]
steel fiber water
felt
Carbon Ni 0.085 Carbon Ni 0.085 A-201, Tokuyama – 1.9 150 50 1 M KOH [51]
paper paper
Ni foam Ni/ Ni/C CuCoO3 LDPE-g-VBC AS-4 2.1 460 50 1% K2CO3 [52]
CeO2–La2O3/C
Cu
Stainless 0.7CO2.3O4 3 Stainless Pt 1 Quaternary 1.8 100 25 1 M KOH [53]
steel steel ammonium
mesh mesh radiation grafted
membrane
Stainless Cu0.7CO2.3O4 3 Stainless Nano Ni 2 mm-qPVBz/Cl- QPVB/Cl- 1.9 100 55 Deionized [54]
steel steel water
mesh mesh
Cu
Stainless 0.7CO2.3O4 3 Stainless Nano Ni 2 QPDTB Poly 1.9 100 50 Deionized [55]
steel steel (DMAEMA- water
mesh mesh co-TFEMA-
co-BMA)
Ni foam Ni/ 40 Carbon CuCoO3 40 Mg–Al layered PTFE 2.2 208 70 0.1 M [56]
CeO2–La2O3/C cloth double hydroxide NaOH/
Na2CO3
Ni foam Ni–Fe Carbon Ni–Mo PSF Quaternary 70 [57]
cloth ammonium
NiO Graphene NiO Graphene Selemion AMV – 1.9 150 80 0–5.36 [58]
KOH
Ni oxide Graphene Ni Graphene Selemion AMV 2 90 30 Deionized [59]
water
Pt coated Ce0.2MnFe1.8O4 3.5 Pt coated Ni 3.5 FAA-3-PK-130 1.8 300 Deionized [60]
Ti Ti water
5
Table 7
Performance comparisons between Alkaline, PEM using pure water, and direct
seawater electrolysis [62].
Electrolysis Energy consumption Efficiency based on Ref.
technology [kWh/kgH2 HHV [%]
PEM electrolysis 47–63 67–82 [63]

Alkaline electrolysis 47–66 62–82 [63]
Direct seawater 50–53 75–79 [64]
electrolysis
Fig. 3. Overpotential losses in a water electrolyzer [94].
hydrogen production water electrolyzers, PEM and AWE, are discussed.

HER occurs at the cathode side of the PEM electrolysis cell. Currently,
Pt-based materials are the most suitable for the PEM cathodes because
they exhibit significant HER activation in acidic electrolytes. Further
more, Pt-based electrocatalysts are considered to be the state–of–the–art
electrochemical catalysts for PEM electrolysis [126,127]. However,
limited availability and the high cost of Pt are the main constraints
limiting its use in large-scale applications. Therefore, the development
of highly active catalysts with high stability is needed to increase the
applicability of PEM electrolyzers. A substantial amount of research has
focused on minimising Pt catalyst loading [128–136]. The high activity
and durability of a Pt@N-containing carbon shell on carbon nanofibers
(Pt@CS/CNF) have been investigated [137]. Figure (9) shows TEM and
XPS images of the improved electrocatalyst as well as Pt/CNTs catalyst
activity [130]. An analysis of density functional theory (DFT) and high
–angle annular dark field scanning transmission electron microscopy
Fig. 1. Energy sources for a net-zero emissions scenario of hydrogen produc (HAADF-STEM) showed a high interaction and electrocatalytic activity
tion for 2020–2050 [71].
between Pt and CNT atoms.
Transition metals have been recently utilized as cathodic electro
4. Electrocatalysts for water electrolysis catalysts, including MoS2, MoSe2 and WS2 [138–149]. MoS2 was fabri
cated according to the Nafion PEM method; the resulting performance of
4.1. PEM water electrolysis hydrogen evolution reaction (HER) and the cathodic HER was an overpotential of 175 mV at a current density of
oxygen evolution reaction (OER) 10 mA [150]. On the electrocatalytic surface, the electronic structure
was improved by cation-doping which increased the hydrogen adsorp
In this subsection, HER and OER catalysts used in the most common tion on the cathode [151,152].
Fig. 2. Hydrogen production costs from renewable electricity (solar PV and wind energy systems) in 2030 [71].
6
Fig. 4. Cell performance versus overpotential.
Fig. 6. PEM water electrolyzer schematic diagram and reaction mecha

nism [114].
Fig. 5. Alkaline water electrolysis technology [114]. Fig. 7. SOEC reaction mechanism [114].
4.1.1. Oxygen evolution reaction electrocatalysts for PEM water electrolysis surface area and thereby achieve high catalytic activity [150,153,154].
The development of OER electrocatalysts has received a significant The ultrafine size of iron nanocrystals and their homogeneous distri
amount of attention to enhance PEM electrolyzer performance. Iron (Ir)- bution are shown in Figure (10a–c). The CNBs enhance the conductivity
based and ruthenium (Ru)-based catalysts are the most common OER and the ultrafine Ir electrocatalyst has a larger surface area which leads
electrocatalysts suitable for PEM electrolyzer acidic environments. The to good stability and a lower overpotential of 290 mV at a current
highest OER electrocatalyst activity is exhibited by Ru-based catalysts, density of 10 mA [11]. Furthermore, the integration between Co oxide
but the stability of Ru catalysts is still lower than Ir-based catalysts [10, and Ir SA gives excellent stability and high OER electrocatalyst activity,
18]. Ir-based electrocatalysts are of significant interest because of their as demonstrated in Figure (10d–f) [13]. Moreover, 3D superstructure
ability to perform in acidic environments, with low overpotential and iron electrocatalyst performance is also presented in Figure (10g-i). A 3D
high stability. The activation of Ir-based electrocatalysts can be Ir catalyst consisting of ultrathin iron nanosheets increases the surface
enhanced by controlling the following parameters: particle size, crystal area and achieves high OER electrocatalyst activation and a low over
structure, morphology, and substrate materials. Utilizing ultrathin or potential of 240 mV [14]. The performance of various OER electro
small Ir-based electrocatalyst particles is a method to increase the catalysts for PEM electrolyzers is summarized in Table (3).
7
reduce the oxidation caused by degradation [39]. In addition, OER was

improved by adding Co(OH)2 nanosheets which leads to self-repairing of
nickel (Ni) electrodes [19]. Furthermore, the use of fluctuating power
such as the direct use of renewable energy increased the cell voltage
because degrades the cell performance [38].
5. Technical barriers to H2 production from impure water
5.1. Technical barriers to anion exchange membrane electrolyzers
Oxygen evolution reaction selectivity: AEM electrolysis is a promising

technology for hydrogen production from water. Primary AEM water
electrolysis components and materials are listed in Table (5). The AEM
electrolyzer cathode and anode operate under alkaline conditions.
Therefore, lower cost (e.g. steel, Ti) and non-Nobel metals (e.g. Fe, Ni, or
Co-based catalysts) can be used to produce hydrogen at lower costs
[155]. Because of the shortage of pure or drinking water, AEM elec
trolysis offers a substantial advantage of being able to utilise impure
water. Thus, the focus in this section is on the technical barriers to
producing hydrogen from impure water via AEM electrolyzers. Water is
supplied to the anode, which diffuses through the membrane to the
cathode based on the concentration gradient. The membrane conducts
the OH− radical generated at the cathode to the anode, and then oxidizes
Fig. 8. AEM reaction mechanism [114].
it into H2O and O2 products. The impurities included in the feedstock
water affect the cathode fouling rates. The membrane permselectivity
4.2. Alkaline water electrolyser catalyst materials for HER and OER should reduce the fouling of cationic impurities [156]. Using seawater in
electrolyzers has also been investigated [62,157,158]. The membrane
The development of new electrode materials is essential for permselectivity is considered a vital parameter to minimize the cation
enhancing AWE performance. The selection of a high resistance reverse impurities effect, which can deposit and block the active membrane
current is an important parameter for catalyst and electrode materials sites.
because of the AWE performance influenced by the reverse current. The The electrolysis of wastewater involves different concerns, such as
performance of various electrode catalyst materials is compared for HER halide reactions and chlorine (Cl) reactivity. The influence of Cl− on the
and OER in Table (4). The durability of catalysts is evaluated and OER has been investigated [159]. Seawater was shown to be unsuitable
considered during the start-up and shut-down operations of AWE elec for PEM water electrolyzers due to co-generation of Cl2 and Br2 [160].
trolyzers [39–44]. Chemical and physical degradation as a result of the The OER reaction is influenced by the more significant chlorine con
reverse current is the main challenge requiring the development of centration to form ClO− ; it also appears on the surface of the catalyst
improved catalyst materials for AWE electrolyzers. The addition of material [161]. Various species are produced by the chlorine reactions;
manganese to Co/phosphate-based catalysts for HER has been shown to Figure (11) presents the chloride and bromide-oxidation reactions for
Fig. 9. a, b) Electocatalyst TEM images, c) XPS analysis of Pt@CS/CNF, d) TEM images after a durability test [137], e) Pt/CNTs synthesis process, f) Pt/CNTs
HAAD-STEM analysis image, and g) HER calculated ΔGH [130].
8
Fig. 10. a) Synthesis process, b) TEM analysis images of Ir@HEDP/CNBs, c) Performance of OER [11], d) Synthesis process of Ir SA electrocatalyst, e) Performance
curve, f) Various catalysts activity versus mass activity [13], g) 3D Ir superstructure synthesis process, h) Performance of OER, i) 3D superstructure performance and
Tafel slopes [14].
the OER [159]. The chlorine reactions exhibit different resulting species. The direct use of natural seawater was investigated, and more
The chlorate reactions depend on the pH of the feedstock water, mass extensive potential results were presented [163]. Different catalyst
transport, and current density. The OER reaction kinetics for impure materials were also studied at the anode and cathode using natural
water still require further investigation. The influence on the AEM cell seawater buffered with pH (7.4), and the activity exceeded the
performance of adding sodium chloride (NaCl) to the electrolyte was HER/OER activity at both electrodes (Ir–C/Pt–C) [164–166]. Therefore,
investigated; the NaCl addition showed a significant decrease in the cell appropriate selection of electrocatalyst materials will help minimize cell
current density and an increase in the electrolyte conductivity [64]. The overpotential. Conventional alkaline and PEM electrolyzers use noble
cell faradaic efficiency operating at a lower current density can reach catalyst metals such as Pt, Ru, and Ir, which will increase the electro
100%; however, Cl− oxidation reduced the efficiency to 93.4% [162]. lyzer cost [105]. Thus, non-noble metal catalyst development has been
The stability of Na+ does not influence AEM cells. Impure and nat investigated to reduce the AEM cell cost [48]. Various OER catalyst
ural salt water poisons cathodes by cationic contamination. In contrast, materials include IrO2, Ni–Fe alloys, Cu0.7CO2.3O4, graphene, and
impure and sea water can be used in AEM and PEM water electrolyzers. Pb2Ru2O6.5, while the HER catalysts include Pt-black, Ni–Mo,
The cell’s performance using natural river water and seawater has been Ni/CeO2–La2O3/C, Ni, CuCoOx, and graphene. Low-cost catalyst mate
investigated [98]. The overpotential of river water was shown to be rials were evaluated and developed for the AEM electrolyzer [48]. The
lower than the resulting overpotential from salt water. loading of the commercial catalysts for OER and HER are Acta 3030
Fig. 11. Chlorine resulting species at the OER [159].
9
(CuCoOx) and Acta 4030 (Ni/CeO2–La2O3/C), respectively. Figure (12)

illustrates the resulting cell voltage at various catalyst material loadings.
The catalyst was measured over the loading range of 0.6–7.4 mg/cm2
[48]; the HER catalyst loading was shown to influence the electrolyzer
potential.
The most significant elements that influence the cell’s performance
are Ca, Na, and Mg; these elements’ contaminations can be removed by
washing. Pure water production from the direct use of a seawater
electrolyzer is the most significant aspect of generating hydrogen and
oxygen, which is then utilized in fuel cells to generate water and elec
tricity. Seawater can be fed into the electrolyzer directly or indirectly
after treatment. The energy consumption by several desalination tech
nologies is shown in Figure (13). The energy consumption of the
reversible seawater was 3,370 kWh/Nm3H2O to generate 1 Nm3H2O [167,
168]. The combined use of a seawater electrolyzer and fuel cell in an
integrated cycle to generate green hydrogen, electricity, and pure water
is investigated. The reversible seawater electrolysis energy consumption
Fig. 13. Energy consumption of various desalination technologies [167,168].
is higher than other established water technologies like reverse osmosis
(RO), multi-stage flash distillation (MSF), multi-effect distillation
(MED), and mechanical vapour compression (MVC). cationic contamination. HER occurs at the cathode, generating negative
Reversible seawater electrolysis can produce large volumes of hydroxyl (OH− ) ions. The impurities in the water influence the con
hydrogen, but the electrolysis technologies should be more interesting. ductivity of the AEM. Table (6) lists the maximum levels of cationic
However, the energy consumption of the seawater electrolyzer was contaminants in drinking water. The higher levels of primary and sec
higher than that for high purity water or RO water. The entire system is ondary elements also have negative effects on the process of splitting
illustrated in Figure (14) including the power demand and production of impure water [61].
pure water from the combination of an electrolyzer and fuel cells. The Furthermore, various chemical degradation pathways of polymer
PV devices can produce renewable electricity, or solar and wind energy development have been studied [170]. The membrane’s physical
can supply the power required by households (city), electrolyzers, and degradation is also accelerated by the use of impure water; in particular,
the RO desalination of seawater to provide pure water. Hydrogen and metal hydroxides can damage the electrolyzer membrane. Contamina
oxygen produced by the electrolyzer can be used at night to generate tion influences mass transport and decreases performance. Ionic
renewable electricity to meet power demands and produce pure water contamination affects the AEM and PEM membranes, leading to
by the fuel cell and desalination process. The water generated from the decreased water transport.
fuel cell is considered pure water and can be fed into the RO process. The Further investigation is needed to increase the membrane perfor
seawater electrolyzer and fuel cell integrated system offers advantages mance using impure water. The membrane permselectivity is the most
by storing renewable electricity as hydrogen and producing purified significant challenge to mitigate the impacts of overpotential resulting
water from seawater and fuel cells. The seawater splitting has recently from the impure water [163]. Electrodialysis has been investigated for
received significant interest; a pre-purification process is also needed to the purification and desalination of various contaminated feedstock
decrease the cation element’s concentrations and remove contaminants. water levels [166,167,171]. Further advancements in membrane design
Consequently, higher energy consumption is required for splitting are required to overcome undesirable impurities and increase the life
seawater into hydrogen and oxygen. time. The direct splitting of the dirty water and seawater by conven
Cationic poisoning is a significant challenge regarding seawater tional alkaline and PEM electrolyzers can be performed under certain
electrolyzers. The presence of cationic contamination can lead to elec conditions.
trolyzer failure. Anodes have been shown to be influenced by higher
cation element concentrations [169]. Cathodes are also affected by 5.2. Technical barriers of PEM stack electrolyzers
PEM electrolyzers split water based on an electrochemical process

into hydrogen and oxygen molecules. The PEM electrolyzers can be used
to generate green hydrogen from renewable electric sources. PEM
electrolyzers have several advantages, including more minor mass vol
ume characteristics, higher hydrogen production purity, and higher
safety levels [172]. A PEM electrolyzer is comprised of an electrolytic
conductor, anode, and cathode. The integration of the anode and cath
ode with the electrolyte is named the membrane electrode assembly
(MEA). In a hydrogen electrolyzer stack, the electric energy is converted
into chemical energy, and the electrons and protons recombine to
generate hydrogen at the cathode, as shown in the cross-sectional
schematic in Figure (15) [95]. The minimum applied voltage to
initiate the water electrolysis reaction corresponds to the sum of the
reversible potential for each semi-reaction at both electrodes.
The basic hydrogen electrolyzer stack layout is presented in
Figure (16). The electrolysis process has been used for many years to
generate hydrogen for the ammonia synthesis process. A commercial
electrolyzer stack can generate high-purity hydrogen using renewable
electricity. The most significant challenge faced by this technology is the
Fig. 12. AEM water electrolysis performance at different HER catalyst availability and cost of pure water as a feedstock for the system. PEM
loading [48]. commercial electrolyzer stack performance was investigated for
10
Fig. 14. The proposed integrated system for meeting power and pure water demands using seawater.
hydrogen production from artificial river water [173]. The commercial at the cathode [174].
PEM electrolyzer, model EHC070 from Enoah Inc., Japan, composed of a Water contaminants influenced the PEM electrolyzer cell voltage,
Nafion membrane and using a noble metal catalyst layer, has been which appeared in the larger cell voltage compared with the pure water.
investigated. The hydrogen electrolyzer stack components are shown in The concentration of higher cation elements decreased the cell effi
Figure (17). The total active area of electrodes was 11.34 cm2. The noble ciency because the electrolyzer efficiency is inversely proportional to the
metal catalysts Pt and IrO2 were utilized for the cathode and anode, electrolyzer’s resulting voltage, meaning that the cell voltage increased
respectively. The protons H+ are passed through the Nafion membrane based on the water contaminants; this leads to lower energy efficiency
from the anode to the cathode side. The effects of the cation element on and higher energy consumption by the electrolyzer [175]. Impure water
the MEA performance were also measured. The influence of the cation can be supplied to the PEM electrolyzer, but it will decrease the cell
elements (Na+, Mg2+, K+, and Ca2+) on the MEA performance can be performance and the durability of the electrolyzer. The performance of
seen in the cell resulting voltage. Figure (18) depicts the resulting cell the cell electrolyzer using different water types with long-term opera
voltage utilizing soft and ultrapure water. The impure water or artificial tion (200 h) is shown in Figure (19). The cell voltage was measured for
soft water cell voltage show a higher voltage than that for the ultrapure 200 h for each tested sample. It was observed that the steady cell voltage
water; the cell voltage substantially increased to 3 V for contaminated was obtained at ¼ soft or river water concentration mixed with ultrapure
water. In contrast, the purified water cell voltage has a constant value of water, then the voltage increased with the operation time because of the
1.8 V. It was clear that the cation elements decreased the conductivity of higher depositing of cations ions on the cell membrane that increased
the MEA, and these elements are replaced with H+ protons. The cell the cell resistance and decreased the membrane conductivity. Moreover,
voltage rapidly increased because of the hydrogen production reaction a lower affinity was exhibited from the monovalent cation ions Na+ and
K+ compared with divalent contaminants that were clearly observed for
the resulting cell voltage.
6. Summary and outlook of the hydrogen production from water

electrolyzers
Most studies of impure water electrolyzers focus on the anode re

actions. However, the electrolyzer’s design should be included in both
electrodes—cathode and anode. AEM and PEM electrolysis cells have
inherent challenges due to the cation element’s concentrations and
poisoning effects. The continuous improvement of the cell performance
is required by using inexpensive materials such as higher catalyst
loading and electrode structure, and maintaining the MEA conductivity
will enhance the electrolyzer performance. Furthermore, the relation
between the catalyst durability and characteristics like morphology,
catalyst phase, and composition should be investigated. The deposition
Fig. 15. PEM electrolyzer cross-sectional view [95].
11
Fig. 16. Basic layout of H2 and O2 production including the electrolyzer.
Fig. 17. Exploded view of a commercial PEM electrolyzer: a) end plates, b) current collectors, c) gaskets, d) gas diffusion layers, e) MEA [173].
Fig. 18. PEM performance at different feeding water types [173].

Fig. 19. PEM cell performance for various feeding water types [173].
12
Fig. 20. The combination of cost reductions in electricity and electrolyzers [114].
of impurities on the catalyst layers and the MEA will reduce the mem with low activity and high stability. Therefore, OER electrocatalysts
brane conductivity and cell durability. All electrolysis systems are needs more attention to enhance the activity of the PEM electrolyzer. In
influenced by water impurities, including dirty water or seawater. addition, commercial-scale PEM electrolysis needs high current den
Therefore, further investigations are required to evaluate the degrada sities, long hours of operation, and high energy efficiency at low volt
tion of the membrane element. Membrane degradation is considered the ages. Several future development and challenges should be considered
main durability parameter; it can lead to faster and more frequent to enhance the alkaline, PEM, and AEM electrolyzer efficiencies, such as
replacement of the membrane and all electrolyzer parts. Table (7) selecting more active catalysts, utilizing less critical raw materials, and
compares the performance analysis of the alkaline and PEM electro utilizing thinner membranes. The current green hydrogen production
lyzers using pure water with the seawater electrolysis results [62]. The can give more flexibility to the power system if the value of that service
electrolyzer energy efficiency with seawater is lower than the impure is sufficiently known and remunerated. The fluctuation of input power
water performance. The comparison was carried out for 1 kg hydrogen to the AWE electrolyzer decreases the performance of the electrolyzer.
production from seawater and pure water. The degradation of the Furthermore, the catalyst degradation is the main challenge of AWE
membrane increases over the impure water, which will lead to higher which caused a reverse current in the start-up and shutdown operations.
hydrogen production costs. Occasionally, the improvement in one parameter leads to a decrease in
The most available water on Earth is seawater from oceans, with a the performance of another; larger membrane thickness will achieve a
seemingly unlimited supply. Nevertheless, the operating and capital longer lifetime but that will increase the membrane transport resistance,
costs of the hydrogen stack electrolyzers are slightly raised by feeding resulting in decreased the cell efficiency. Further development should be
impure water to the cell. The current study investigated the impure pursued for anion exchange membranes by testing new materials to
water (seawater and river water) effect on AEM and PEM electrolyzers, avoid the undesirable effect of the cation elements. Also, highly efficient
respectively. Hydrogen production from impure water by electrolyzers HER and OER catalysts should be used, such as Co3O4 on multi-walled
is the most attractive technology for electrochemical, hydrogen con carbon nanotubes [176]. In addition, the physical development of the
version, and storage technology. The combination between hydrogen MEA degradation will increase the electrochemical characteristics and
fuel cells and a reversible seawater electrolyzer can produce electricity thermal stability. Using non-noble metal catalyst materials can reduce
and manage water demands. The resulting pure water from this system the system capital cost, but the AEM’s performance is still low and must
will be used to fulfil the household demand. be increased to be applicable for large-scale hydrogen production.
Renewable hydrogen production via an electrolyzer requires water However, the cost of PEM stack electrolyzers is still greater than for
and energy. The electrolysis system has less water footprint using about alkaline, and both have untapped economic cost decreasing issues.
9 kg of water per kgH2. The power supply cost can be reduced by Hydrogen production by the AEM technology can use less expensive
combining electricity and electrolyzer cells. Figure (20) illustrates future material than that used historically. Therefore, the AEM technology has
cost reductions in the electrolysis systems [114]. The long-term com a cost reduction potential compared with PEM technology. The perfor
bination of electricity and electrolyzer systems can lead to an 80% mance of the PEM electrolyzer stack can also be enhanced by reducing
reduction of green hydrogen production costs. the membrane thickness, redesigning the catalyst-coated electrodes, and
using inexpensive catalyst materials. It can also be concluded that the
7. Conclusion higher AEM mechanical stability and ion conductivity are the most
significant challenges. Lastly, ionic conductivity plays an important role
This work provided a comprehensive review of the available water in AEM performance.
electrolysis technologies. The catalyst materials of PEM, AWE, and AEM
water electrolyzers were investigated. PEM water electrolysis and HER Declaration of competing interest
and OER electrocatalysts still have different obstacles to obtain high cell
efficiency. The most popular HER electrocatalyst materials for a PEM The authors declare that they have no known competing financial
electrolyzer is Pt-based catalysts but the activity still requires more interests or personal relationships that could have appeared to influence
effort to meet the high performance and practical PEM electrolyzer the work reported in this paper.
application targets. Moreover, OER electrocatalysts mainly use IrO2
13
Data availability [22] Y. Wang, L. Zhang, K. Yin, J. Zhang, H. Gao, N. Liu, Z. Peng, Z. Zhang,
Nanoporous iridium-based alloy nanowires as highly efcient electrocatalysts
toward acidic oxygen evolution reaction, ACS Appl. Mater. Interfaces 11 (2019)
Data will be made available on request. 39728–39736.
[23] Q. Shi, C. Zhu, H. Zhong, D. Su, N. Li, M.H. Engelhard, H. Xia, Q. Zhang, S. Feng,
Acknowledgments S.P. Beckman, D. Du, Y. Lin, Nanovoid incorporated IrxCu metallic aerogels for
oxygen evolution reaction catalysis, ACS Energy Lett. 3 (2018) 2038–2044.
[24] Y. Pi, Q. Shao, P. Wang, J. Guo, X. Huang, General Formation of monodisperse
The author would like to thank Prof. Shinji Kambara (Environ IrM (M = Ni Co, Fe) bimetallic nanoclusters as bifunctional electrocatalysts for
mental and Renewable Energy Systems department-Gifu University acidic overall water splitting, Adv. Funct. Mater. 27 (2017), 1700886.
[25] H. Guo, Z. Fang, H. Li, D. Fernandez, G. Henkelman, S.M. Humphrey, G. Yu,
Japan), and Prof. Yoshiaki Kawajiri (Institutes of Innovation for Future Rational design of rhodium-iridium alloy nanoparticles as highly active catalysts
Society, Nagoya University) for their kind support. for acidic oxygen evolution, ACS Nano 13 (2019) 13225–13234.
[26] J. Xu, Z. Lian, B. Wei, Y. Li, O. Bondarchuk, N. Zhang, Z. Yu, A. Araujo,
I. Amorim, Z. Wang, B. Li, L. Liu, Strong electronic coupling between ultrafne
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Hydrogen Production by Water Electrolysis - A Review

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Results in Engineering 20 (2023) 101426

Contents lists available at ScienceDirect

Hydrogen production by water electrolysis technologies: A review

E-mail address: [email protected].

Table 1 generating high-purity hydrogen. PEM water electrolysis technology

Technology maturity Mature Commercial R&D R&D

Cathode: 2H+ + 2e− → H2 (Urev = 0.00 V) (2)

Anode Cathode Membrane Ionomer

GDL Catalyst Loading GDL Catalyst Loading Voltage Current T

PEM electrolysis 47–63 67–82 [63]

Fig. 3. Overpotential losses in a water electrolyzer [94].

hydrogen production water electrolyzers, PEM and AWE, are discussed.

Fig. 4. Cell performance versus overpotential.

Fig. 6. PEM water electrolyzer schematic diagram and reaction mecha­

reduce the oxidation caused by degradation [39]. In addition, OER was

5. Technical barriers to H2 production from impure water

5.1. Technical barriers to anion exchange membrane electrolyzers

Oxygen evolution reaction selectivity: AEM electrolysis is a promising

Fig. 11. Chlorine resulting species at the OER [159].

(CuCoOx) and Acta 4030 (Ni/CeO2–La2O3/C), respectively. Figure (12)

PEM electrolyzers split water based on an electrochemical process

6. Summary and outlook of the hydrogen production from water

Most studies of impure water electrolyzers focus on the anode re­

Fig. 16. Basic layout of H2 and O2 production including the electrolyzer.

Fig. 18. PEM performance at different feeding water types [173].

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Fig. 6. PEM water electrolyzer schematic diagram and reaction mecha

Most studies of impure water electrolyzers focus on the anode re