Hydrogen Production by PEM Water Electrolysis - A Review

Materials Science for Energy Technologies 2 (2019) 442–454
Contents lists available at ScienceDirect
Materials Science for Energy Technologies

CHINESE ROOTS
GLOBAL IMPACT
journal homepage: www.keaipublishing.com/en/journals/materials-science-for-energy-technologies
Hydrogen production by PEM water electrolysis – A review

S. Shiva Kumar, V. Himabindu ⇑
Centre for Alternative Energy Options, Institute of Science and Technology, Jawaharlal Nehru Technological University Hyderabad, Kukatpally, Hyderabad, Telangana 500085, India
a r t i c l e i n f o a b s t r a c t
Article history: Hydrogen is the most efficient energy carrier. Hydrogen can be obtained from different sources of raw
Received 9 January 2019 materials including water. Among many hydrogen production methods, eco-friendly and high purity of
Revised 15 March 2019 hydrogen can be obtained by water electrolysis. However, In terms of sustainability and environmental
Accepted 15 March 2019
impact, PEM water electrolysis was considered as most promising techniques for high pure efficient
Available online 29 March 2019
hydrogen production from renewable energy sources and emits only oxygen as byproduct without any
carbon emissions. Moreover, the produced hydrogen (H2) and oxygen (O2) directly used for fuel cell
Keywords:
and industrial applications. However, overall water splitting resulting in only 4% of global industrial
Hydrogen production
PEM water electrolysis
hydrogen being produced by electrolysis of water, mainly due to the economic issues. Nowadays,
Electrocatalysts increased the desire production of green hydrogen has increased the interest on PEM water electrolysis.
Hydrogen evolution reaction (HER) Thus the considerable research has been completed recently in the development of cost effective electro-
Oxygen evolution reaction (OER) catalysts for PEM water electrolysis. In this present review, we discussed about the recent developments
in the PEM water electrolysis including high performance low cost HER and OER electrocatalysts and
their challenges new and old related to electrocatalysts and PEM cell components also addressed. This
review will contribute further research improvements and a road map in order to support in developing
the PEM water electrolyser as a commercially feasible hydrogen production purpose.
Ó 2019 The Authors. Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-
nd/4.0/).
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 443
2. Water electrolysis technologies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444
3. Alkaline water electrolysis (AWE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444
4. Solid oxide electrolysis (SOE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445
5. Microbial electrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445
6. PEM water electrolysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445
6.1. Principle of PEM water electrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 446
6.2. Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 446
6.3. Faradaic efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447
6.4. PEM water electrolysis cell components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447
6.4.1. Membrane electrode assemblies (MEAs). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447
6.4.2. Current collectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 448
6.4.3. Separator plates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 448
6.5. Electrocatalysts for PEM water electrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 449
6.5.1. Electrocatalysts for hydrogen evolution reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 449
6.5.2. Electrocatalysts for oxygen evolution reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 450
⇑ Corresponding author.
E-mail addresses: [email protected], [email protected] (V. Himabindu).
Peer review under responsibility of KeAi Communications Co., Ltd.
Production and hosting by Elsevier
https://doi.org/10.1016/j.mset.2019.03.002
2589-2991/Ó 2019 The Authors. Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
S. Shiva Kumar, V. Himabindu / Materials Science for Energy Technologies 2 (2019) 442–454 443
7. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 451
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 451
Conflict of interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 451
Appendix A. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 451
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 451
1. Introduction gasses [31–33]. Further, the unremittingly growing the global

energy needs and the limited reserves of fossil fuels together with
Nowadays global energy consumption was increased gradually sustainability and environmental impact need to be develop new
due to the growing the population and standards of living style. energy approaches without any carbon emissions. Nowadays has
Moreover, with increasing the global warming and environmental taken attention as an environmental friendly energy strategies
pollution, the development of renewable energy sources was which possibly to replace the current fossil fuel based energy pro-
becoming more essential. Hydrogen is one of the most promising duction [34], this can be achieved by when the hydrogen is pro-
clean and sustainable energy carriers and emits only water as a duced from the renewable water. Among many hydrogen
byproduct without any carbon emissions [1]. Hydrogen having production methods, eco-friendly and high purity of hydrogen
many attractive properties as an energy carriers and high energy (99.999%) can be obtained from electrolysis of water to produce
density (140 MJ/kg) which is more than two times higher than typ- pure hydrogen and oxygen it is called as water electrolysis. The
ical solid fuels (50 MJ/kg) [2]. Presently, the entire worldwide basic reaction is described in Eq. (1).
hydrogen production is around 500 billion cubic meter (b m3) per
year [3,4]. The produced hydrogen is mostly used in many indus- 1
1H2 O þ Electricity 237:2kJ:mol
trial applications, such as fertilizers, petroleum refining processes,
1
petrochemical, fuel cells, and chemical industries [5–8]. Hydrogen þ Heat 48:6 kJ:mol H2 þ 1=2 O2 ð1Þ
has been produced from various renewable and non-renewable
energy resources such as fossil fuels, especially steam reforming However, hydrogen production efficiency through water elec-
of methane [9–11], oil/naphtha reforming [12–14], coal gasifica- trolysis is very low to be economically competitive due to the high
tion [15–17], biomass [18–21], biological sources [22–25] and energy consumption and low hydrogen evolution rate. Therefore in
water electrolysis (WE) [26–28]. The various comprehensive order to increase the efficiency and reduce the energy consump-
hydrogen production methods (Fig. 1) along with their advantages, tion, many researchers have been done their work related to devel-
disadvantages, efficiency and capital cost are provided in Table 1. opment of alternative low cost electrocatalysts, efficiency and
Currently 96% of the global hydrogen production from non- energy reduction. In this review, various hydrogen production
renewable fossil fuels, in particular steam reforming of methane methods from renewable energy sources along with recent devel-
[29,30]. However, the usage of fossil fuels, they produces lower opments on efficiency, durability, cost effective electrocatalysts
purity of hydrogen with high concentration of harmful greenhouse and its challenges have been discussed and summarized.
Fig. 1. Various Hydrogen Production Methods.

444 S. Shiva Kumar, V. Himabindu / Materials Science for Energy Technologies 2 (2019) 442–454
Table 1
Various Hydrogen production methods along with their advantages, disadvantages efficiency and cost [Refs. [2,4,5]].
Hydrogen Advantages Disadvantages Efficiency Cost [$/kg]

production Method
Steam Reforming Developed technology & Existing infrastructure Produced CO, CO2 Unstable supply 74–85 2.27
Partial Oxidation Established technology Along with H2 Production, produced heavy oils and 60–75 1.48
petroleum coke
Auto thermal Well established technology & Existing infrastructure Produced CO2 as a byproduct, use of fossil fuels. 60–75 1.48
Reforming
Bio photolysis Consumed CO2, Produced O2 as a byproduct, working Low yields of H2, sunlight needed, large reactor required, 10–11 2.13
under mild conditions. O2 sensitivity, high cost of material.
Dark Fermentation Simple method, H2 produced without light, no Fatty acids elimination, low yields of H2, low efficiency, 60–80 2.57
limitation O2, CO2-neutral, involves to waste recycling necessity of huge volume of reactor
Photo Fermentation Involves to waste water recycling, used different low efficiency, Low H2 production rate, sunlight required, 0.1 2.83
organic waste waters, CO2-neutral. necessity of huge volume of reactor, O2-sensitivity
Gasification Abundant, cheap feedstock and neutral CO2. Fluctuating H2 yields because of feedstock impurities, 30–40 1.77–2.05
seasonal availability and formation of tar.
Pyrolysis Abundant, cheap feedstock and CO2-neutral. Tar formation, fluctuating H2 amount because of feedstock 35–50 1.59–1.70
impurities and seasonal availability
Thermolysis Clean and sustainable, O2-byproduct, copious High capital costs, Elements toxicity, corrosion problems. 20–45 7.98–8.40
feedstock
Photolysis O2 as byproduct, abundant feedstock, No emissions. Low efficiency, non-effective photocatalytic material, 0.06 8–10
Requires sunlight.
Electrolysis Established technology Zero emission Existing Storage and Transportation problem. 60–80 10.30
infrastructure O2 as byproduct
2. Water electrolysis technologies mechanism as shown in Fig. 2. Alkaline electrolysis operates at

lower temperatures such as 30–80 °C with aqueous solution
Electrolysis of water is one such most capable method for pro- (KOH/NaOH) as the electrolyte, the concentration of the electrolyte
duction of hydrogen because uses renewable H2O and produced is 20% to 30% [37,47–49]. In alkaline water electrolysis process,
only pure oxygen as by-product. Additionally, in electrolysis pro- asbestos diaphragm and nickel materials are used as the electrodes
cess utilizes the DC power from sustainable energy resources for [39]. The diaphragm having in the middle of the cell and it is sep-
example solar, wind and biomass. But, at present only R 4% of arates the cathode and anode also separates the produced gases
hydrogen can be obtained by electrolysis of water mainly due to from their respective electrodes and avoiding the mixing of pro-
the economic issues [35,36]. It is expected to this value is increased duced gases electrolysis process. However, in alkaline electrolysis
in the near in future although increase the usage of renewable have negative aspects such as limited current densities (below
energy (solar, wind, nuclear), meanwhile the European Energy 400 mA/cm2), low operating pressure and low energy efficiency
Directive has been fix the goal to utilize 14% of the energy require-
ments from renewable energy sources by 2020 [34]. Furthermore,
water electrolysis having tough advantages such as high cell effi-
ciency and greater hydrogen production rate with high purity this
is more advantage for its further conversion in to electrical energy
using low temperature fuel cells [26]. In electrolysis process, water
molecule is the reactant it is dissociated into hydrogen (H2) and
oxygen (O2) under the influence of electricity. Water electrolysis
can be classified in to the four types based on their electrolyte,
operating conditions, and ionic agents (OH, H+, O2), however
operating principles are both the cases same. The four kinds of
electrolysis methods are (i) Alkaline water electrolysis (AWE)
[37–39], (ii) Solid oxide electrolysis (SOE) [40,41] (iii) Microbial
electrolysis cells (MEC) [170,173]. (iv) PEM water electrolysis
[34,42].
3. Alkaline water electrolysis (AWE)
Hydrogen production by alkaline water electrolysis is well

established technology up to the megawatt range for commercial
level in worldwide and the phenomenon first introduced by
Troostwijk and Diemann in 1789 [43–46]. Alkaline water electrol-
ysis process initially at the cathode side two molecules of alkaline
solution (KOH/NaOH) were reduced to one molecule of hydrogen
(H2) and two hydroxyl ions (OH) are produced. The produced
H2 eliminate from the cathode surface to recombine in a gaseous
form and the hydroxyl ions (OH) transfer under the influence of
the electrical circuit between anode and cathode through the por-
ous diaphragm to the anode, here in discharged to ½ molecule of
oxygen (O2) and one molecule of water (H2O). The O2 recombined
at the surface of electrode and escapes as hydrogen, the following Fig. 2. Schematic illustration of alkaline water electrolysis.
[37,50]. Finally, a new approach in the alkaline electrolysis is under

development of anion exchange membranes (AEM) made up of
polymers with anionic conductivity instead of asbestos diaphragm.
This innovative technology appears to be interesting in the field of
alkaline water electrolysis [51–56].
4. Solid oxide electrolysis (SOE)
The solid oxide electrolysis (SOE) first introduced by Donitz and

Erdle in the 1980s [45,58]. Solid oxide electrolysis has attracted an
abundant deal of attention due to the electrical energy converts
into the chemical energy along with producing the ultra-pure
hydrogen with greater efficiency [57,59]. Solid oxide electrolysis
operates at high pressure and high temperatures 500–850 °C and
utilizes the water in the form of steam. Solid oxide electrolysis pro-
cess conventionally uses the O2 conductors which are mostly
from nickel/yttria stabilized zirconia [60], operating principle of
SOE has shown Fig. 3. Nowadays, some of the ceramic proton con-
ducting materials have been developed and studied in solid oxide
fuel cells. However, increasing the much attention towards ceramic
proton conducting materials for SOE electrolysis process, due to
these materials demonstrates high efficiency and superior ionic
conductivity than O2 conductors at an operating temperature of
500–700 °C [34]. The main characteristics of solid oxide electroly-
sis (SOE) technology is higher operating temperature which makes
Fig. 4. Schematic illustration of Microbial Electrolysis.
advantageous compared to low temperature electrolysis. Although,
the SOE having some issues related to lack of stability and degrada-
tion, which have to be solved before going to commercialization on
a large scale [41,61–63]. mass and wastewaters and this MEC technology is closely related
to microbial fuel cells (MFCs) but operational principle is reverse
of MFCs [170].
5. Microbial electrolysis
The first Microbial electrolysis cell (MEC) approach is intro-
duced by two independent research organizations such as Penn
Hydrogen production by Microbial electrolysis cell (MEC) tech-
state university and Wageningen University, Netherlands in 2005
nology can be achieved by organic matter including renewable bio-
[170,171]. In microbial electrolysis cells (MECs), electrical energy
converted into chemical energy. MECs produced hydrogen from
organic materials in the influence of electric current. In microbial
electrolysis process, initially in anode side the substrate is oxidized
by microbes and then produces CO2, protons and electrons. The
electrons are moving through the external circuit to cathode side
and the protons are travelled to cathode via proton conducting
membrane (electrolyte) whereas the protons and electrons com-
bined with produces the hydrogen. Fig. 4 shows the principle of
MEC. MEC process some electrochemical potential is produced
during the oxidation in the anode side is insufficient to give
decreased voltage required for the hydrogen evolution reaction at
the cathode side hence it required extra voltage (0.2 V–1.0 V).
Therefore MEC process required small amount of external voltage
when compared to water electrolysis [172]. However, this MEC
technology is still under development and having several chal-
lenges towards hydrogen production rate, high internal resistance,
electrode materials and complicated design need to be addressed
before and commercialization of this technology [173].
6. PEM water electrolysis
The first PEM water electrolysis was idealized by Grubb in the

early fifties and General Electric Co. was developed in 1966 to
overcome the drawbacks to the alkaline water electrolysis
[64–66,68,69]. PEM water electrolysis technology is similar to the
PEM fuel cell technology, where solid polysulfonated membranes
(NafionÒ, fumapemÒ) was used as a electrolyte (proton conductor)
[57,67,70,71]. These proton exchange membranes having many
advantages such as lower gas permeability, high proton conductiv-
Fig. 3. Schematic illustration of Solid Oxide electrolysis. ity (0.1 ± 0.02 S cm1), lower thickness (R20–300 mm) and
high-pressure operations. In terms of sustainability and environ-

mental impact, PEM water electrolysis is one of the favorable
methods for conversion of renewable energy to high pure hydro-
gen. Another promising PEM water electrolysis has great advan-
tages such as compact design, high current density (above
2 A cm2), high efficiency, fast response, small footprint, operates
under lower temperatures (20–80 °C) and produced ultrapure
hydrogen and also produced oxygen as a byproduct [70–74], also
described in Table 2 Additionally, balancing PEM electrolysis plants
is very simple, which is more attractive for industrial applications.
The state-of-the-art electrocatalysts for PEM electrolysis are high
activity of noble metals such as Pt/Pd as the hydrogen evolution
reaction (HER) at the cathode [73–75] and IrO2/RuO2 as the oxygen
evolution reaction (OER) at the anode [76–82], which makes the
more expensive than alkaline water electrolysis. Therefore, one of
the main challenges in PEM water electrolysis is to reduce the pro-
duction cost and to maintain the high efficiency. Since then, sub-
stantial research has been devoted to improve the PEM water
electrolysis components, and as a result, this technology is
approaching commercial markets [57].
6.1. Principle of PEM water electrolysis
In PEM water electrolysis, water is electrochemically split into

hydrogen and oxygen at their respective electrodes such as hydro-
gen at the cathode and oxygen at the anode. PEM water electrolysis
is accrued by pumping of water to the anode where it is spilt into
oxygen (O2), protons (H+) and electrons (e). These protons are
traveled via proton conducting membrane to the cathode side. Fig. 5. Schematic illustration of PEM water electrolysis.
The electrons exit from the anode through the external power cir-
cuit, which provides the driving force (cell voltage) for the reaction. The reversible voltage can be calculated by the following Eq. (3).
At the cathode side the protons and electrons re-combine to pro-
DG
duce the hydrogen, the following mechanism as shown in Fig. 5. Erev ¼ ¼ 1:23V ð3Þ
nF
However, at the time of water splitting some entropy generated.
6.2. Thermodynamics
Thus, it is more suitable to employ enthalpy (DH) in its place of DG
for the potential calculation. Therefore at the standard conditions,
Electrolysis process water is split in to hydrogen and oxygen, for
the change of enthalpy is DH = 285.84 kJ mol1 and change of
this water splitting some energy is required at the same time the
Gibbs free enthalpy is DG = 237.22 kJ mol1 [83,84]. Therefore,
equal energy released during the formation of water molecule form
the minimum required voltage (VTN) for the water electrolysis
gases of hydrogen and oxygen. Therefore the minimum required
can be calculated by following Eq. (4).
energy for water splitting can be calculated from Gibbs free (DG)
energy. Standard conditions, Gibbs free energy for the splitting of DH DG TDS
V TN ¼ ¼ þ ¼ 1:48V ð4Þ
water into hydrogen and oxygen can be calculated by following nF nF nF
Eq. (2).
Where
DG ¼ nFErev ð2Þ
VTN = thermo-neutral voltage
Where DS = change in entropy
T = temperature
n = no. of electrons involved
F = 96500 (Faraday’s constant) According to the first law of thermodynamics energy is con-
Erev = Reversible voltage served. Thus, the conversion efficiency calculated from the yields
Table 2
Advantages and Disadvantages of different water electrolysis technologies.
Electrolysis process Advantages Disadvantages

Alkaline Electrolysis Well established technology Non-noble electro catalysts Low cost Low current densities Formation of carbonates on the electrode
technology The energy efficiency is (70–80%) Commercialized decreases the performance of the electrolyser Low purity of gases
Low operational pressure (3–30 bar) Low dynamic operation
Solid Oxide Electrolysis Higher efficiency (90–100%) Non-noble electro catalysts High Laboratory stage Large system design Low durability
working Pressure
Microbial Electrolysis Used different organic waste waters Under development Low hydrogen production rate Low purity of
hydrogen
PEM Electrolysis High current densities Compact system design and Quick Response New and partially established High cost of components Acidic
Greater hydrogen production rate with High purity of gases (99.99%) environment Low durability Commercialization is in near term
Higher energy efficiency (80–90%) High dynamic operation
of converted electrical energy into chemical energy. Typically, The theoretical volume of gas can be calculated by the Faraday’s
water electrolysis efficiency is calculated by the higher heating second low, based on the current density, electrolysis time and
value (HHV) of hydrogen. Since the electrolysis process water is electrode area by assuming a 100% Faradaic efficiency, as shown
supplied to the cell in liquid phase efficiency can be calculated in Eq. (7). When the practical amount produced in the experiment
by the following Eq. (5). can be measured by water-gas displacement method or gas chro-
matography analysis.
VTN
g¼ ð5Þ ! c
Vcell 103 ml tð60sÞ I s
V H2 ¼ VM ðlÞ ð7Þ
Where l min 2FðC:Þ
VTN = Thermo-neutral voltage Where VH2 indicates the yield of theoretical hydrogen, VM is the

Vcell = Cell voltage ideal gas expression VM ¼ Rð273þT
P
, R indicates the ideal gas con-
stant (0.082 l atm K1 mol1), T denotes the temperature, P means
Therefore, the water electrolyser efficiency can be calculated by
presser (atm), t is time (s), I is the applied current (A) and F indi-
any current density. Since operating the lower current densities at
cates the Faraday’s constant (96,485 C.mol1).
lower voltages, the electrolyser efficiency becomes higher [85].
6.3. Faradaic efficiency 6.4. PEM water electrolysis cell components
In water electrolysis, faradaic efficiency is a one of the quantita- The major PEM water electrolysis cell components are mem-
brane electrode assemblies (MEAs), current collectors (gas diffu-
tive analysis which is useful for to determine the how many elec-
trons are transported in the external circuit to the surface of sion layers), and separator plates. Typical overview of PEM water
electrolysis cell assembly was shown in Fig. 6. However, heart of
electrode for conducting the electrochemical reaction either oxy-
gen evolution reaction (OER) or hydrogen evolution reaction the electrolysis cell is MEA which is separated the cell in to two
half cells (anode and cathode).
(HER) and other electrochemical reactions in the electrolytes.
Therefore, the faradaic efficiency can be defined as the ratio
between experimentally evolved volume of gas value (hydrogen 6.4.1. Membrane electrode assemblies (MEAs)
or oxygen) and theoretically calculated volume of gas value, as The membrane electrode assemblies are consisting of mem-
shown in Eq. (6) brane, ionomer solution and anode, cathode electrocatalysts which
is responsible 24% of overall cell cost (Fig. 7). Membrane is back
VH2 ðProducudÞ
gfaraday ¼ ð6Þ bone of the PEMWE cell, the most commonly used membranes
VH2 ðCalculatedÞ are Perfluorosulfonic acid polymer membranes such as NafionÒ,
Fig. 6. (a) Overview of typical PEM water electrolysier (b) PEM cell stack (c) Cell components; 1-Bipolar plate, 2-Anode current collector, 3-MEA, 4-Cathode current collector.
Fig. 7. Breakdown capital cost of PEM water electrolyser (13 kg day1), Reprinted from Ref. [2].
FumapemÒ, FlemionÒ, and AciplexÒ [83,86]. These membranes and separator plates. Therefore current collectors are plays a signif-
have unique properties such as high strength, high efficiency and icant role on overall mechanism of PEM water electrolysis and cell
high oxidative stability, dimensionally stabile with change of tem- efficiency. The current collectors have must be corrosion resis-
peratures, good durability and high proton conductivity. However, tance, good electrical conductivity due to the acidic environment,
currently NafionÒ membranes (NafionÒ 115, 117, and 212) are high over potential and presence of oxygen. The current collectors
mostly used in PEM water electrolysers because NafionÒ mem- also deliver good mechanical strength to the membrane. Moreover,
branes have tough advantages such as operating at higher current current collectors have an optimized porosity and pore volumes
densities (2 A/cm2), high durability, high proton conductivity and due to the produced gases are effectively expelled and water must
good mechanical stability [45]. Typically the membrane electrode be reaching the catalytic sites of electrode surface, therefore opti-
assemblies are fabricated by different methods, but most of mized current collectors are required, the optimized parameters
researchers are followed catalyst coated on membrane (CCM) of current collectors are described in Table 3. Typically in PEM
method, in this method the electrocatalyst slurry is directly coated water electrolysis pours titanium plates are using as promising
on the surface of membrane and then hot pressed at 120 °C tem- current collectors due to the these materials having unique proper-
perature with 60 kg cm2 pressure [166,167]. The electrocatalysts ties such as good electrical conductivity, mechanical stability and
are employed to promote the charge transfer kinetics in order to corrosion resistant under acidic medium [168]. The porous tita-
decrease the activation energy of water electrolysis method. nium plates act as current collectors and gas diffusion layer
The homogeneous electrocatalyst slurry was prepared by using (GDL) for both sides of the MEA and enclosed by bipolar plates fol-
appropriate amounts of electrocatalyst along with ionomer solu- lowed by gaskets. The current collectors were used to allow the
tion (eg. NafionÒ ionomer), isopropanol and water followed by son- electrical current to flow between the electrodes and bipolar plates
ication about 30 min. The addition of ionomer solution with ionic [87–89]. In many studies titanium grids/meshes/felts, carbon cur-
transport properties in the catalytic layers has two different on rent collectors and stainless steel grids are used, but the electro-
the electrodes in the PEM water electrolysis. The ionomer is pro- chemical performance is lower than pours titanium plates.
moting the proton transport from the electrode layers to the mem-
brane thus increasing the cell efficiency by decreasing the cell 6.4.3. Separator plates
ohmic losess. Further the ionomer solution act as a binder, which In typical PEM water electrolysis separator plates and current
is gives the dimensionally stable structure of the catalyst and pro- collectors are responsible for the 48% (Fig. 7) of overall cell cost
viding the mechanical stability subsequently durability of the elec- and a linear donor to the required cell voltage. Presently, the
trodes [57]. On the other hand with increasing the ionomer PEM water electrolysis separator plates made up titanium, stain-
content, it reduces the electrical conductivity due to the ionomer less steel and graphite but these materials were high cost and hav-
is electron resistant. Therefore, the optimization of the ionomer ing different operational drawbacks. This is under the drawbacks
content is necessary. also essential reduction of cost that the research and development
of the separator plates are facing the major challenges. Moreover,
the separator plates surface structure was more essential for the
6.4.2. Current collectors
PEM water electrolysis cell, they must be provision conduction
In PEM water electrolysis process water is pumping to the
path of pumping water and produced gases out of the electrolysis
anode size of the PEM cell where oxygen evolution reaction
cell [90–92]. Many electrolysers systems, different designs of sep-
accrues, the feed water travels through the separator plates and
arator plates are using for better performance however the straight
diffuses via current collectors. The feed water reaches the electrode
surface and the water molecule is decomposed into oxygen, pro-
tons and electrons. The oxygen was return to out of the cell Table 3
through electrode surface, current collectors then separator plates. Parameters of current collector for PEM water electrolysis [Ref. [3]].
The protons are moving from the anode electrode surface to cath- Current collector thickness 0.8–2 mm
ode side through the proton conducting membrane. The electrons Electrical Resistance 5–10 mO cm
are travelled from the current collectors, separator plates than Gas permeability 1 1013–1 1011 m2
moving to the cathode side, after reaching the electrode surface Porosity 20–50%
Pore size 5–30 mm
recombined with protons to gives the hydrogen. The obtained
Particle size 25–250 mm
hydrogen was leaving from the cell via cathode current collector
parallel flow field design was shown promising electrochemical costs by increasing the specific performance and durability of the
activity especially in PEM water electrolysis [169]. Typically tita- electrocatalysts. Although for economic viability it is necessary to
nium materials give outstanding strength, high thermal conductiv- decrease the Pt loading on carbon or to find out the alternative
ity, low permeability and low resistivity but anode side (oxygen) to Pt based electrocatalysts [100,101]. The electrochemical active
titanium material corrodes and grows inert oxide layer. Therefore surface area is generally developed by the dispersed carbon
decrease the performance of the electrolyser. To address these nanoparticles in order to enhance the surface area and thereby
issues and protect the titanium plates precious metal coatings decrease the Pt loadings [102,103]. The electrocatalyst was then
and alloys have been studied. This coating are drastically decreased hosted in gas diffusion electrodes based on large surface area cost
the corrosion rate but this extra process, precious coating materials effective electronic carriers such as carbon nanotubes/carbons
and also expensive base titanium. Therefore cost effective separa- black. Later on many researchers initiated to use of different car-
tor plates are still under challenges. bon blacks (CB) as support materials for platinum based catalyst
as a standard electrocatalyst towards the HER [57]. Though, the
lower Pt loading on carbons are still indicates the significant por-
6.5. Electrocatalysts for PEM water electrolysis
tion of the overall system value, mainly due to the performance
degradation or corrosion of the carbon support. Nowadays, cathode
Typically, in PEM water electrolysis noble metal based electro-
side metal loading were maintained approximately 0.5–1 mg cm2
catalysts are used such as Pt/Pd-based catalysts as cathode towards
and further decreases will be always needed for the potential val-
the hydrogen evolution reaction (HER) and RuO2/IrO2 catalysts as
ues reaching below 0.2 mg cm2. Further, Badwal et al. reported on
anode for oxygen evolution reaction (OER) [57,93–96]. The first
the development of PEM water electrolyser system for producing
PEM water electrolysis research article published by Russell
high pure oxygen and hydrogen. The electrolyser was operated at
et al., in the year of 1973 at general electric company using the
2 bar pressure with 75–85 °C temperature. The Nafion 112 and
PEM electrolysis cell. In this study experimental results have
115 membranes were used as electrolyte and Pt/C with loading
shown considerably efficient and the obtained performance of
of up to 0.4 mg cm2 and various noble metal catalysts with metal
1.88 Vat an operating current of 1 A cm2 and 2.24 V at 2 A cm2
loading of 0.2–0.4 mg cm2 were maintained for cathode and
with cell life of 15,000 h without any degradation performance
anode respectively [104]. Giddey et al. studied 20 wt% Pt/C as cath-
[57,97]. However, the cost of PEM electrolysis was high due to
ode electrode and Ir, Ru as anode electrocatalysts along with an
the use of expensive materials despite these drawbacks PEM elec-
electrode surface area of 50–150 cm2 coated on Nafion 115 mem-
trolysis has numerous advantages for example high operating cur-
brane. The noble metal loading varied between 0.2 and
rent densities, high purity of gases and high efficiency. Later on to
0.4 mg cm2 and operated the electrolyser at 20 bar pressure and
address these drawbacks several researchers much effort focused
at 70–80 °C temperature [105].
on inexpensive PEM electrolysis methods and developed many
Later on, several researchers have been developed various alter-
alternative electrocatalysts based on improving the efficiency and
native electrocatlysts and studied towards the hydrogen evolution
stability of the low cost Ru-based multi-metallic oxides also reduc-
reaction. For example, Hinnemann et al. studied MoS2 electrocata-
ing the usage of the high cost metals (Ir, Pt) using the alternative
lyst for the HER [106]. These studies have been carried out by fab-
active carbon supports have been developed and reported, as
ricating the MEA with MoS2/graphite and standard Pt, the obtained
shown in Fig. 8, which are discussed in the following paragraphs
results have demonstrated that MoS2 has an acceptable catalyst for
and some of the results have been summarized in Table 3.
HER, though potentially lower current densities (10 mA cm2 at
175 mV) than conventional Pt cathodes. Corrales-Sánchez et al.
6.5.1. Electrocatalysts for hydrogen evolution reaction reported the performance of three different types of MoS2-based
The challenges towards hydrogen evolution reaction (HER) in electrodes such as bare pristine MoS2, MoS2 mixed with commer-
PEM electrolysis were focused on to development of electrocata- cial conductive carbon, VulcanÒ XC72, and MoS2 on reduced gra-
lysts for the cathode. In most of the previous reports, typically plat- phene (MoS2/rGO) with the anode of IrO2. The obtained results of
inum (Pt) based materials have been used as a standard catalyst for the pristine MoS2 was shown worst performance the achieved cur-
the hydrogen evolution reaction [57,98,99] due to the Pt gives the rent density of approximately 0.02 A/cm2 at 1.9 V. Later, their best
excellent HER activity and exhibits outstanding stability in acidic performing MoS2/rGO electrode achieved a current density of
environment but highly dispersed carbon supported Pt-based 0.1 A cm2, while the best mixture of MoS2 and VulcanÒ (47 wt%
materials are currently benchmark catalysts for HER in PEM water MoS2) reached almost 0.3 A cm2 at 1.9 V. The MoS2 mixed carbon
electrolysis [57]. However, these platinum based catalysts are shown superior electrocatalytic performance towards the HER but
more expensive, therefore most of the research has been mainly only comparative to the other MoS2 electrocatalysts still not com-
focused on to decrease the cost of electrocatalysts and operational parable to Pt based catalysts [106]. Further in order to increase the
hydrogen production rates and current density recently Sarno M
et al. synthesized RuS2@MoS2 electrocatalyst and studied experi-
mentally for hydrogen evolution reaction. The synthesized RuS2@-
MoS2 catalyst revealed outstanding properties such as high
exchange current density, acceptable over potential and Volmer-
Tafel behavior (36 mV dec1). Because of high contact of RuS2
boundaries on the MoS2 with robust d character of RuS2 and elec-
trical conductivity of these two materials were grown together
which lead the responsible for the high production of hydrogen
yields (10.2 l/h) at an operated current density of 1.1 A cm2 with
utilization of 41.8 W power with 3.8 KWh/Nm3 of energy con-
sumption and 93% efficiency [107].
Nowadays Pd based electrocatalysts have shown increasing the
significant interest towards the hydrogen evolution reaction
Fig. 8. Number of scientific reports on OER and HER from 2005 to 2017 (Reprinted because, palladium which is earth abundant and low cost com-
from Ref. [153]). pared to platinum, also shows remarkable electrocatalytic activity
for several oxidation and reduction reactions [108–110]. For exam- enhance the stability of RuO2 [129–131]. Li, G. et al. prepared
ple, S.A. Grigoriev et al. has been experimentally studied Pd/ and experimentally studied bimetallic oxide of IrxRu1xO2 electro-
VulcanXC-72 and Pt/VulcanXC-72 for the HER, the attained results catalyst as the anode in PEM water electrolysis. From the electro-
of Pd/VulcanXC-72 has shown slightly less efficient than those chemical results, it was observed that the increased
obtained with Pt/VulcanXC-72 [111]. Pd activated carbon also electrochemical performance was achieved with the subsequent
tested for the HER with different weight loadings but unfortunately addition of RuO2, the cell voltage of 1.676 V at an operating current
the obtained performance has not compared with the conventional density of 1 A cm2. Meanwhile, the physicochemical studies
Pt electrodes. The Pd carbon nanotubes (Pd/CNTs) have also been demonstrated the increased surface area, pore volume and average
evaluated towards the HER though acceptable difference has not pore size of the electrocatalyst also with increasing the Ru concen-
obtained compared to Pt/CNTs [112,113]. Carbon nanotubes are tration in IrxRu1xO2 along with increased the rutile crystallinity
generally used as an electron carrier support material for noble [132]. Kalliopi M. Papazisi et al. synthesized IrxPt1xO2 electrocat-
metal catalysts since they are generally known as having superior alysts by modified Adams fusion method and studied electrochem-
electron conductivity and corrosion resistance than conventional ical performance and stability towards the OER. The attained
carbon blacks. Afterward, to better electrocatalytic activity and sta- results of IrxPt1xO2 electrocatalysts have been revealed the stable
bility, hetero atom (N, P, S and B) doped carbon nanoparticles have electro chemical activity towards the OER in PEM water electroly-
been wildly used as an electron carrier support material for noble sis. The electrochemical performance of IrxPt1xO2 along with their
metal electrodes in oxygen reduction reactions and hydrogen evo- durability and large surface area are quite advantageous for the
lution reactions [114–118]. Ramakrishna et al. studied palladium development of low cost electrocatalysts for OER [133]. However,
supported on N- doped CNTs electrocatalyst (Pd/N-CNTs) towards in order to reduce the cost and limited resources of Ir, it is required
the hydrogen evolution reaction and compared with commercial to reduce or replace the Ir usage in electrocatalysts by using the
Pt/C. The obtained Pd/N-CNTs results have shown comparable elec- other non-noble metal oxides. Therefore significant research
trocatalytic activity than commercial Pt/C towards the HER [100]. efforts focused at reducing noble metal content by mixing transi-
Shiva Kumar et al. reported experimental studies on phosphorus tion metal oxides with IrO2 and/or RuO2, such as TiO2 [134–137],
(P) doped graphene (Pd/PG) and P-doped carbon nanoparticles SnO2 [78,138], Ta2O5 [119,139], Nb2O5 [140], Sb2O5 [141], PbO2
(Pd/P-CNPs) for the HER and compared with the conventional Pt/ [142], MnO2 [143,144] and other mixed oxides also studied for
CB. The attained results have exhibited almost similar electro- OER [81,145–147], some of the experimental results have been dis-
chemical performance than conventional Pt/CB. Hence, Pd- based cussed following paragraphs and summarized in Table 4.
electrocatalysts can be used alternative to Pt-based catalysts for Vinod Kumar et al. A bimetallic RuxNb1xO2 electrocatalyst was
the HER [83,120]. synthesized by Adams, and hydrolysis methods also studies
In order to further reduce the cost of HER catalysts produced by towards OER. The Adams method found to be better mixture of
using the other carbon-supported electrocatalysts, especially those RuO2 with Nb2O5 and influenced the electrochemical properties.
only consist of earth abundant materials and low cost, such as A- The attained results have been demonstrated increased stability
Ni-C, Mo2C/CNTs, Ni2P/CNTs, Co-doped FeS2/CNTs, WO2/C nano- with the addition of 20% Nb2O5 to RuO2 in Adams method. Further
wires and CoFe nanoalloys encapsulated in N-doped graphene there is no improvement in electrocatalytic activity with increasing
etc., have been extensively studied in potential HER electrocata- the Nb2O5 content of above 20% owing to the dilution of active
lysts for alternative to Pt [121–126]. However, these carbon- material [148]. Ardizzone et al. experimentally studied nanostruc-
supported Pt free HER catalysts that have actually been tested in tured SnO2-IrO2-TaO5 oxides as a promising electrocatalyst for
PEM water electrolysis are rarely reported. In summary, in PEM OER. The SnO2-IrO2-TaO5 electrocatalyst has shown better electro
water electrolysis alternative to Pt-based catalysts for HER several analytical properties, the main role of tantalum for increasing the
electrocatalysts have been developed and studied towards the surface area with charge storage capacity and enhancing the elec-
HER. However, most of the catalysts belong to the main family of trical conductivity. Meanwhile SnO2-IrO2-Ta2O5 has shown better
metals with support of nano carbons have been developed. Among electrochemical performance towards the OER in acidic environ-
these catalysts MoSx and Pd-based nano carbons appears to be the ment [149]. Further, to reduce the noble metal content and
most capable electrocatalysts in terms of electro catalytic activity improve the stability Thomas Audichon et al. suggested trimetallic
and stability. Ru0.8Ir(0.2x)CexO2 electrocatalyst towards the OER. In this study,
effect of cerium (Ce) content in Ru0.8Ir(0.2x)CexO2 electrocatalyst
6.5.2. Electrocatalysts for oxygen evolution reaction was studied for determining the electrochemical performance
The state-of-the-art, metal oxides are used as an electrocata- and stability by cyclic voltammetry method in acidic medium.
lysts for oxygen evolution reaction (OER) in PEM water electrol- The attained results have shown the addition of cerium is not
yser. However, among these metal oxides IrO2 and RuO2 have effected on stability. Therefore, the addition of cerium only permits
shown higher metallic conductivity which is of 104 cm1 O1 also the reducing the Ir and Ru content without destroying the OER per-
in these oxides metal-metal distance value and the radius of the formance. Furthermore, the oxygen mobility in cerium crystallo-
cations are overlapping of the inner d-orbital is feasible, the elec- graphic nature may participate to enhancing the electrocatalytic
trons of d-orbitals in these d-bands are responsible for the electron activity of active sites [150].
conductivity [127]. Therefore RuO2 has shown the better OER per- Datta, M.K. et al. experimentally studied F doped Thin film
formance among the other metal oxides [57,76], Although RuO2 (Sn0.8Ir0.2) O2 electrocatalyst as an potential OER electrode in
more active than IrO2 but poor stability due to the corrosion from PEM water electrolysis. The electrocatalytic activity of F doped
the strong acidity at the perfluorosulfonic membrane and high Thin film (Sn0.8Ir0.2) O2 increased with increasing the F loading
anodic potential at OER, other hand IrO2 is most resistive material along with increased electrochemical performance such as polar-
to OER in acidic environment but lower performance [128]. To ization resistance, Tafel slope, efficiency and stability at an opti-
address these drawbacks with the purpose of to enhance the stabil- mum percentage of 10 wt% of F. The prepared (Sn0.8Ir0.2) O2:10F
ity with high efficiency and decreasing the cost, in these directions electrocatalyst showing remarkably similar electrochemical per-
researchers in the recent years initiated developing the different formance and improved stability compared to pure IrO2 [151].
substitute catalysts for the OER. When it comes to economic feasi- Furthermore, recent investigations by S.D. Ghadge et al. sug-
bility and better stability, need to be addition of IrO2 in order to gested one dimensional vertically aligned nanotubes of (Sn0.8Ir0.2)
Table 4
Historical Results of Different Electrocatalysts in PEM Water Electrolysis.
anode catalyst cathode catalyst anode loading (mg/cm2) cathode loading (mg/cm2) membrane Temp (°C) Voltage at 1 A/cm2 Ref.
Ir-Black 40% Pt/GNF 2.0 0.8 Nafion-115 90 1.67 [113]
Ir-Black 40% Pt/XC-72 2.0 0.8 Nafion-115 90 1.70 [113]
Ir-Black Pt40/Vulcan XC-72 2.4 0.7 Nafion-115 90 1.66 [72]
Ir-Black Pd40/Vulcan XC-72 2.4 0.7 Nafion-115 90 1.70 [72]
Ir-Black Pt-black 2.0 0.8 Nafion-117 90 1.71 [156]
IrO2 Pt-black 2.0 2.5 Nafion-115 80 1.60 [157]
RuO2 40% Pt/C 10 0.4 Nafion-115 – 1.88 [158]
RuO2 30% Pt/C 3.0 0.5 Nafion-112 80 1.65 [160]
RuO2 30% Pt/C 1.5 0.5 Nafion-1035 80 1.63 [159]
IrO2 30% Pt/C 1.5 0.5 Nafion-1035 80 1.67 [159]
IrO2 60% Pt/C 3.0 0.5 Nafion-115 80 1.58 [161]
IrO2 30% Pt/C 2.5 0.5 Nafion-115 80 1.7 [162]
Ir-Black Pt/CNT 2.4 – Nafion-115 90 1.72 [112]
Ru0.7Ir0.3O2 40% Pt/C 2.5 0.5 Nafion-117 80 1.70 [154]
IrO2/SnO2 40% Pt/C 1.5 0.5 Nafion-212 80 1.57 [155]
RuO2/SnO2 40% Pt/C 30. 0.6 Nafion-115 80 1.723 [155]
RuO2 40% Pt/C 3.0 0.6 Nafion-115 80 1.74 [155]
RuO2 30%Pd/N-CNT 3.0 0.7 Nafion-115 80 1.84 [100]
RuO2 30%Pd/P-CNPs 3.0 0.7 Nafion-115 80 2 [82]
RuO2 30%Pd/PG 3.0 0.7 Nafion-115 80 1.95 [120]
RuO2 30%Pd/PN-CNPs 3.0 0.7 Nafion-115 80 1.90 [163]
Ru0.8Pd0.2O2 30% Pt/CB 3.0 0.7 Nafion-115 80 2.03 [164]
Ir0.6Ru0.4O2 20% Pt/C 2.04 2.04 Nafion-115 80 1.56 [154]
RuO2 46% Pt/C 1.0 0.2 Nafion-117 80 1.68 [165]
Ru0.9Ir0.1O2 46% Pt/C 1.0 0.2 Nafion-117 80 1.75 [165]
Ru0.7Ir0.3O2 46% Pt/C 1.6 0.2 Nafion-117 80 1.80 [165]
Ru0.3Ir0.7O2 46% Pt/C 1.4 0.2 Nafion-117 80 1.74 [165]
IrO2 46% Pt/C 1.2 0.2 Nafion-117 80 1.80 [165]
O2:10F as a promising OER electrode for PEM water electrolysis. The Acknowledgements
synthesized Sn0.8Ir0.2O2:10F–NTs electrocatalyst exhibited better
electrochemical performance with significantly 2.5 times more elec- The authors are thankful to Bhabha Atomic Research Centre
trocatalytic activity compared to IrO2 and Sn0.8Ir0.2O2:10F – Thin (BARC), Board of Research in Nuclear Science (BRNS), Deportment
films electrocatalyst. Moreover, the synthesized Sn0.8Ir0.2O2:10F– of Atomic Energy, Government of India for providing financial
NTs exhibits outstanding electrochemical stability in the harsh assistance (Sanction order No. 2013/36/21/BRNS/1739).
acidic environment. Additionally, Sn0.8Ir0.2O2:10F–NTs electrocata-
lyst has shown higher mass (21.67 A g1), superior electrochemical
surface area (38.46 m2 g1), specific activity (0.005633 mA cm2), Conflict of interest
lower charge transfer resistance (R4.2 O cm2) and lower Tafel slop
(58.8 mV dec-1) compared to the as-synthesized IrO2 and Sn0.8Ir0.2- On behalf of all authors, the corresponding author states that
O2:10F -Thin film based electrocatalysts [152]. Finally conclude that, there is no conflict of interest.
mixed metal oxides are contributes to enhance the efficiency and
stability against corrosion and additionally they degreasing the cost
of electrocatalysts. Appendix A. Supplementary data
Supplementary data to this article can be found online at

https://doi.org/10.1016/j.mset.2019.03.002.
7. Conclusion
In this review, we have discussed a short introduction about the References

various hydrogen production techniques and their advantages and
disadvantages. In addition, have mainly focus on the recent devel- [1] A. Kazim, T.N. Veziroglu, Utilization of solar hydrogen energy in the UAE to
maintain its share in the world energy market for the 21st century, Renewable
opment of PEM water electrolysis including their HER, OER electro- Energy 24 (2001) 259–274.
catalysts for water splitting and highlighting the most efficient [2] Jun Chi, Yu. Hongmei, Water electrolysis based on renewable energy for
electrocatalysts among similar materials. The present review not hydrogen production, Chin. J. Catal. 39 (2018) 390–394.
[3] C. Acar, I. Dincer, Comparative assessment of hydrogen production methods
only discussed the present state-of-the-art also elaborated the in- from renewable and non-renewable methods, Int. J. Hydrogen Energy 39
depth investigations of historical research, challenges and recent (2014) 1–12.
achievements on PEM water electrolysis. In particular attention [4] D.A.J. Rand, A journey on the electrochemical road to sustainability, J. Solid
State Electrochem. 15 (2011) 1579–1622.
has also paid to the electrocatalysts that are more efficient and [5] A. Züttel, Hydrogen storage methods, Naturwissenschaften 91 (2004) 157–
stable at large current densities in HER and OER, which have been 172.
remarkably advanced to show outstanding electrocatalytic activity [6] M.A. Rakib, J.R. Grace, C.J. Lim, S.S.E.H. Elnashaie, B. Ghiasi, Steam reforming of
propane in a fluidized bed membrane reactor for hydrogen production, Int. J.
and stability at higher current densities. Therefore in PEM water
Hydrogen Energy 35 (2010) 6276–6290.
electrolysis considerable achievements have been made in emerg- [7] H. Lim, Hydrogen selectivity and permeance effect on the water gas shift
ing robust and stable electrocatalysts for commercial criteria. reaction (WGSR) in a membrane reactor, Korean J. Chem. Eng. 32 (2015)
Finally, we outlined our idea for future research direction it should 1522–1527.
[8] B. Lee, H. Chae, N.H. Choi, C. Moon, S. Moon, H. Lim, Economic evaluation with
be proceed in order to improve renewable energy based PEM elec- sensitivity and profitability analysis for hydrogen production from water
trolysers should be more cost effective approach. electrolysis in Korea, Int. J. Hydrogen Energy 42 (2017) 6462–6471.
[9] A. Boyano, A.M. Blanco-Marigorta, T. Morosuk, G. Tsatsaronis, [40] M. Ni, M.K.H. Leung, D.Y.C. Leung, Technological development of hydrogen
Exergoenvironmental analysis of a steam methane reforming process for production by solid oxide electrolyzer cell (SOEC), Int. J. Hydrogen Energy 33
hydrogen production, Energy 36 (2011) 2202–2214. (2008) 2337–2354.
[10] J. Xu, L. Chen, K.F. Tan, A. Borgna, M. Saeys, Effect of boron on the stability of [41] M.A. Laguna-Bercero, Recent advances in high temperature electrolysis using
Ni catalysts during steam methane reforming, J. Catal. 261 (2009) 158–165. solid oxide fuel cells: a review, J. Power Sources 203 (2012) 4–16.
[11] D.A.J.M. Ligthart, R.A. Van Santen, E.J.M. Hensen, Influence of particle size on [42] A.S. Arico, S. Siracusano, N. Briguglio, V. Baglio, A. Di Blasi, V. Antonucci,
the activity and stability in steam methane reforming of supported Rh Polymer electrolyte membrane water electrolysis: status of technologies and
nanoparticles, J. Catal. 280 (2011) 206–220. potential applications in combination with renewable power sources, J. Appl.
[12] R. Trane, S. Dahl, M.S. Skjøth-Rasmussen, A.D. Jensen, Catalytic steam Electrochem. 43 (2013) 107–118.
reforming of bio-oil, Int. J. Hydrogen Energy 37 (2012) 6447–6472. [43] S. Trasatti, Water electrolysis: who first, J. Electroanal. Chem. 479 (1999) 90–
[13] D. Iranshahi, E. Pourazadi, K. Paymooni, M.R. Rahimpour, A. Jahanmiri, B. 91.
Moghtaderi, A dynamic membrane reactor concept for naphtha reforming, [44] M. Balat, Potential importance of hydrogen as a future solution to
considering radial flow patterns for both sweeping gas and reacting environmental and transportation problems, Int. J. Hydrogen Energy 33
materials, Chem. Eng. J. 178 (2011) 264–275. (2008) 4013–4029.
[14] M.R. Rahimpour, M. Jafari, D. Iranshahi, Progress in catalytic naphtha [45] M. Carmo, L. David Fritz, J. Mergel, D. Stolten, A comprehensive review on
reforming process: a review, Appl. Energy 109 (2013) 79–93. PEM water electrolysis, Int. J. Hydrogen Energy 38 (2013) 4901–4934.
[15] J. Huang, I. Dincer, Parametric analysis and assessment of a coal gasification [46] A. Ursua, L.M. Gandia, P. Sanchis, Hydrogen production from water
plant for hydrogen production, Int. J. Hydrogen Energy 39 (2014) 3294–3303. electrolysis: current status and future trends, Proc. IEEE 100 (2) (2012)
[16] S.S. Seyitoglu, I. Dincer, A. Kilicarslan, Energy and exergy analyses of 410–426.
hydrogen production by coal gasification, Int. J. Hydrogen Energy 42 (2017) [47] S. Seetharamana, R. Balaji, K. Ramya, K.S. Dhathathreyan, M. Velan, Graphene
2592–2600. oxide modified non-noble metal electrode for alkaline anion exchange
[17] P. Burmistrz, T. Chmielniak, L. Czepirski, M. Gazda-Grzywacz, Carbon membrane water electrolyzers, Int. J. Hydrogen Energy 38 (2013) 14934–
footprint of the hydrogen production process utilizing subbituminous coal 14942.
and lignite gasification, J. Cleaner Prod. 139 (2016) 858–865. [48] P.H. Vermeiren, W. Adriansens, J.P. Moreels, R. Leysen, Evaluation of the
[18] T.N. Veziroglu, F. Barbir, Hydrogen Energy Technologies, UNIDO, Vienna, ZirfonÒ separator for use in alkaline water electrolysis and Ni-H2 batteries,
1998. Int. J. Hydrogen Energy 23 (1998) 321–324.
[19] M.A. Mujeebu, Hydrogen and syngas production by superadiabatic [49] D. Burnat, M. Schlupp, A. Wichser, B. Lothenbach, M. Gorbar, A. Züttel, U.F.
combustion-a review, Appl. Energy 173 (2016) 210–224. Vogt, Composite membranes for alkaline electrolysis based on polysulfone
[20] Y. Kalinci, A. Hepbasli, I. Dincer, Biomass-based hydrogen production: a and mineral fillers, J. Power Sources 291 (2015) 163–172.
review and analysis, Int. J. Hydrogen Energy 34 (2009) 8799–8817. [50] S. Marini, P. Salvi, P. Nelli, R. Pesenti, M. Villa, M. Berrettoni, et al., Advanced
[21] A. Abuadala, I. Dincer, A review on biomass-based hydrogen production and alkaline water electrolysis, Electrochim. Acta 82 (2012) 384–391.
potential applications, Int. J. Energy Res. 36 (2012) 415–455. [51] O. Takashi, T. Kenjiro, T. Katsuyuki, A. Katsuhiro, Nickel oxide water
[22] D.B. Levin, L. Pitt, M. Love, Biohydrogen production and limitations to electrolysis diaphragm fabricated by a novel method, Int. J. Hydrogen
practical application, Int. J. Hydrogen Energy 29 (2004) 173–185. Energy 32 (2007) 5094–5097.
[23] D. Das, T.N. Veziroglu, Hydrogen production by biological processes: a survey [52] B. Chakrabarty, A.K. Ghoshal, M.K. Purkait, Preparation, characterization and
of literature, Int. J. Hydrogen Energy 26 (2001) 13–28. performance studies of polysulfone membranes using PVP as an additive, J.
[24] O. Elsharnouby, H. Hafez, G. Nakhla, M.H. El Naggar, A critical literature Membr. Sci. 315 (2008) 36–47.
review on biohydrogen production by pure cultures, Int. J. Hydrogen Energy [53] S. Seetharaman, S. Ravichandran, D.J. Davidson, S. Vasudevan, G. Sozhan,
38 (2013) 4945–4966. Polyvinyl alcohol based membrane as separator for alkaline water
[25] P. Sivagurunathan, G. Kumar, S.H. Kim, T. Kobayashi, K.Q. Xu, W. Guo, et al., electrolyzer, Sep. Sci. Technol. 46 (2011) 1563–1570.
Enhancement strategies for hydrogen production from wastewater: a review, [54] G.J. Hwang, S.G. Lim, S.Y. Bong, C.H. Ryu, H.S. Choi, Preparation of anion
Curr. Org. Chem. 20 (2016) 2744–2752. exchange membrane using polyvinyl chloride (PVC) for alkaline water
[26] F. Barbir, PEM electrolysis for production of hydrogen from renewable energy electrolysis, Korean J. Chem. Eng. 32 (2015) 1896–1901.
sources, Sol. Energy 78 (2005) 661–669. [55] A. Marinkas, I. Struźyńska-Piron, Y. Lee, A. Lim, H.S. Park, J.H. Jang, H.J. Kim, J.
[27] O. Atlam, M. Kolhe, Equivalent electrical model for a proton exchange Kim, A. Maljusch, O. Conradi, D. Henkensmeier, Anion-conductive
membrane (PEM) electrolyser, Energy Convers. Manage. 52 (2011) 2952– membranes based on 2-mesitylbenzimidazolium functionalised poly-(2,6-
2957. dimethyl-1,4-phenylene oxide) and their use in alkaline water electrolysis,
[28] S. Siracusano, V. Baglio, N. Briguglio, G. Brunaccini, A. Di Blasi, A. Ornelas, E. Polymer 145 (2018) 242–251.
Trifoni, V. Antonucci, A.S. Arico, An electrochemical study of a PEM stack for [56] K.C. Sandeep, Sachin Kamath, Krunal Mistry, M. Ashok Kumar, S.K.
water electrolysis, Int. J. Hydrogen Energy 37 (2012) 1939–1946. Bhattacharya, Kalyan Bhanja, Sadhana Mohan, Experimental studies and
[29] Boreum Lee, Juheon Heo, Sehwa Kim, Choonghyun Sung, Changhwan Moon, modeling of advanced alkaline water electrolyser with porous nickel
Sangbong Moon, Hankwon Lima, Economic feasibility studies of high electrodes for hydrogen production, Int. J. Hydrogen Energy 42 (2017)
pressure PEM water electrolysis for distributed H2 refueling stations, 12094–12103.
Energy Convers. Manage. 162 (2018) 139–144. [57] W. Xu, K. Scott, The effects of ionomer content on PEM water electrolyser
[30] A. Borgschulte, The hydrogen grand challenge, Front. Energy Res. 4 (2016) 11, membrane electrode assembly performance, Int. J. Hydrogen Energy 35
https://doi.org/10.3389/fenrg.2016.00011. (2010) 12029–12037.
[31] J.D. Holladay, D.L. King, Y. Wang, An overview of hydrogen production [58] W. Dönitz, E. Erdle, High-temperature electrolysis of water vapor-status of
technologies, Catal. Today 139 (2009) 244–260. development and perspectives for application, Int. J. Hydrogen Energy 10
[32] S. Damyanova, B. Pawelec, K. Arishtirova, J.L.G. Fierro, Ni-based catalysts for (1985) 291–295.
reforming of methane with CO2, Int. J. Hydrogen Energy 37 (2012) 15966– [59] A. Brisse, J. Schefold, M. Zahid, High temperature water electrolysis in solid
15975. oxide cells, Int. J. Hydrogen Energy 33 (2008) 5375–5382.
[33] Md. Mamoon Rashid, Mohammed K. AlMesfer, Hamid Naseem, Md. Danish, [60] M. Liang, B. Yu, M. Wen, J. Chen, J. Xu, Y. Zhai, Preparation of LSM-YSZ
Hydrogen production by water electrolysis: a review of alkaline water composite powder for anode of solid oxide electrolysis cell and its activation
electrolysis, PEM water electrolysis and high temperature water electrolysis, mechanism, J. Power Sources 190 (2009) 341–345.
Int. J. Eng. Adv. Technol. 4 (2015) 2249–8958. [61] P. Moçoteguy, A. Brisse, European Institute for Energy Research (EIFER),
[34] M. Foteini Sapountzi, M. Jose Gracia, C.J. (Kees-Jan) Weststrate, O.A. Hans Emmy-Noeth, A review and comprehensive analysis of degradation
Fredriksson, J.W. (Hans) Niemantsverdriet, Electrocatalysts for the generation mechanisms of solid oxide electrolysis cells, Int. J. Hydrogen Energy 38
of hydrogen, oxygen and synthesis gas, Prog. Energy Combust. Sci. 58 (2017) (2013) 15887–15902.
1–35. [62] J. Rostrup-Nielsen, L.J. Christiansen, Concepts in Syngas Preparation, Catalytic
[35] G. Cipriani, V. Di Dio, F. Genduso, D. La Cascia, R. Liga, R. Miceli, et al., Science Series, Imperial College Press, London, 2011.
Perspective on hydrogen energy carrier and its automotive applications, Int. J. [63] R. Knibbe, M.L. Traulsen, A. Hauch, S.D. Ebbesen, M. Mogensen, Solid oxide
Hydrogen Energy 39 (2014) 8482–8494. electrolysis cells: degradation at high current densities, J. Electrochem. Soc.
[36] S. Dunn, Hydrogen futures: toward a sustainable energy system, Int. J. 157 (2010) B1209–B1217.
Hydrogen Energy 27 (2002) 235–264. [64] W.T. Grubb, Batteries with solid ion exchange electrolytes. 1. Secondary cells
[37] K. Zeng, D. Zhang, Recent progress in alkaline water electrolysis for hydrogen employing metal electrodes, J. Electrochem. Soc. 106 (1959) 275–278.
production and applications, Prog. Energy Combust. Sci. 36 (2010) 307–326. [65] W.T. Grubb, L.W. Niedrach, Batteries with solid ion-exchange membrane
[38] S. Shiva Kumar, S.U.B. Ramakrishna, S. Vijaya Krishna, K. Srilatha, B. Rama electrolytes. 2. Low-temperature hydrogen-oxygen fuel cells, J. Electrochem.
Devi, V. Himabindu, Synthesis of Titanium (IV) oxide composite membrane Soc. 107 (1960) 131–135.
for Hydrogen Production through alkaline water electrolysis, South African, J. [66] J.H. Russell, L.J. Nuttall, A.P. Fickett, Hydrogen generation by solid polymer
Chem. Eng. 25 (2018) 54–61. electrolyte water electrolysis, Am. Chem. Soc. Div. Fuel Chem. Preprints 18
[39] S. Shiva Kumar, S.U.B. Ramakrishna, D. Srinivasulu Reddy, D. Bhagawan, V. (1973) 24–40.
Himabindu, Synthesis of Polysulfone and zirconium oxide coated asbestos [67] A.H. Abdol Rahim, Alhassan Salami Tijani, S.K. Kamarudin, S. Hanapi, An
composite separators for alkaline water electrolysis, Int. J. Chem. Eng. Process overview of polymer electrolyte membrane electrolyzer for hydrogen
Technol. 3 (2017) 1035/1-6. production: Modeling and mass transport, J. Power Sources 309 (2016) 56–65.
[68] S.Z. Baykara, A brief overview on its sources, production and environmental [97] C. Rozain, P. Millet, Electrochemical characterization of polymer electrolyte
impact, Int. J. Hydrogen Energy (2018) 1–10. membrane water electrolysis cells, Electrochim. Acta 131 (2014) 160–167.
[69] Md Arif Khan, H. Zhao, W. Zou, Z. Chen, W. Cao, J. Fang, J. Xu, L. Zhang, J. [98] S. Giancola, M. Zatoń, Á. Reyes-Carmona, M. Dupont, A. Donnadio, S.
Zhang, Recent progresses electrocatalysts for water electrolysis, Electrochem. Cavaliere, J. Rozière, D.J. Jones, Composite short side chain PFSA membranes
Energy Rev. (2018). for PEM water electrolysis, J. Membr. Sci. (2018).
[70] H.K. Jua, S. Badwalb, S. Giddey, A comprehensive review of carbon and [99] S. Siracusano, V. Baglio, F. Lufrano, P. Staiti, A.S. Arico, Electrochemical
hydrocarbon assisted water electrolysis for hydrogen production, Appl. characterization of a PEM water electrolyzer based on a sulfonated
Energy 231 (2018) 502–533. polysulfone membrane, J. Membr. Sci. 448 (2013) 209–214.
[71] P. Nikolaidis, A. Poullikkas, A comparative overview of hydrogen production [100] S.U.B. Ramakrishna, D. Srinivasulu Reddy, S. Shiva Kumar, V. Himabindu,
processes, Renewable Sustainable Energy Rev. 67 (2017) 597–611. Nitrogen doped CNTs supported Palladium electrocatalyst for hydrogen
[72] S.A. Grigoriev, P. Millet, V.N. Fateev, Evaluation of carbon supported Pt and Pd evolution reaction in PEM water electrolyser, Int. J. Hydrogen Energy 41
nanoparticles for the hydrogen evolution reaction in PEM water electrolysers, (2016) 20447–20454.
J. Power Sources 177 (2008) 281–285. [101] S. Martin, P. Garcia-Ybarra, J. Castillo, Ten-fold reduction from the state-of-
[73] S.A. Grigoriev, V.I. Porembsky, V.N. Fateev, Pure hydrogen production by PEM the-art platinum loading of electrodes prepared by electrospraying for high
electrolysis for hydrogen energy, Int. J. Hydrogen Energy 31 (2006) 171–175. temperature proton exchange membrane fuel cells, Electrochem. Commun.
[74] P. Millet, R. Ngameni, S.A. Grigoriev, N. Mbemba, F. Brisset, A. Ranjbari, et al., 93 (2018) 57–61.
PEM water electrolyzers: from electrocatalysis to stack development, Int. J. [102] E.A. Katherine, J.N. Rennera, N. Danilovica, J.X. Wangb, Z. Yu, R. Maricc, H. Yu,
Hydrogen Energy 35 (2010) 5043–5052. Pathways to ultra-low platinum group metal catalyst loading in proton
[75] J. Cheng, V. Zhang, G. Chen, Y. Zhang, Study of IrxRu1-xO2 oxides as anodic exchange membrane electrolyzers, Catal. Today 262 (2016) 121–132.
electrocatalysts for solid polymer electrolyte water electrolysis, Electrochim. [103] B.-S. Lee, H.-Y. Park, I. Choi, M.K. Cho, H.-J. Kim, S.J. Yoo, D. Henkensmeier, J.Y.
Acta 54 (2009) 6250–6256. Kim, S.W. Nam, S. Park, K.-Y. Lee, J.H. Jang, Polarization characteristics of a
[76] M.H.P. Santana, L.A. De Faria, Oxygen and chlorine evolution on RuO2 + TiO2 + low catalyst loading PEM water electrolyzer operating at elevated
CeO2+ Nb2O5 mixed oxide electrodes, Electrochim. Acta 51 (2006) 3578– temperature, J. Power Sources 309 (2016) 127–134.
3585. [104] S.P.S. Badwal, S. Giddey, F.T. Ciacchi, Hydrogen and oxygen generation with
[77] V. Baglio, A. Di Blasi, T. Denaro, V. Antonucci, A.S. Arico, R. Ornelas, et al., polymer electrolyte membrane (PEM) based electrolytic technology, Ionics
Synthesis, characterization and evaluation of IrO2-RuO2 electrocatalytic 12 (2006) 7–14.
powders for oxygen evolution reaction, J New Mater. Electr. Syst. 11 (2008) [105] S. Giddey, F.T. Ciacchi, S.P.S. Badwal, High purity oxygen production with a
105–108. polymer electrolyte membrane electrolyser, J. Membr. Sci. 346 (2010) 227–
[78] X. Wu, J. Tayal, S. Basu, K. Scott, Nano-crystalline RuxSn1-xO2 powder catalysts 232.
for oxygen evolution reaction in proton exchange membrane water [106] B. Hinnemann, P.G. Moses, J. Bonde, K.P. Jorgensen, J.H. Nielsen, S. Horch,
electrolysers, Int. J. Hydrogen Energy 36 (2011) 14796–14804. et al., Biornimetic hydrogen evolution: MoS2 nanoparticles as catalyst for
[79] A.J. Terezo, E.C. Pereira, Preparation and characterization of Ti/RuO2-Nb2O5 hydrogen evolution, J. Am. Chem. Soc. 127 (15) (2005) 5308–5309.
electrodes obtained by polymeric precursor method, Electrochim. Acta 44 [107] M. Sarno, E. Ponticorvo, High hydrogen production rate on RuS2@MoS2 hybrid
(1999) 4507–4513. nanocatalyst by PEM electrolysis, Int. J. Hydrogen Energy (2018).
[80] B. Liu, C. Wang, Y. Chen, Surface determination and electrochemical behavior [108] B.T. Xuan Lam, M. Chiku, E. Higuchi, H. Inoue, Preparation of PdAg and PdAu
of IrO2-RuO2- SiO2 ternary oxide coatings in oxygen evolution reaction nanoparticle-loaded carbon black catalysts and their electrocatalytic activity
application, Electrochim. Acta 264 (2018) 350–357. for the glycerol oxidation reaction in alkaline medium, J. Power Sources 297
[81] R. Kotz, S. Stucki, Stabilization of RuO2 by IrO2 for anodic oxygen evolution in (2015) 149–157.
acid media, Electrochim. Acta 31 (1986) 1311–1316. [109] S. Sarkar, S.C. Peter, An overview on Pd based electrocatalysts for hydrogen
[82] S. Shiva Kumar, S.U.B. Ramakrishna, B. Rama Devi, V. Himabindu, Phosphorus evolution reaction, Inorg. Chem. Front. (2018), https://doi.org/10.1039/
doped carbon nanoparticles supported palladium electrocatalyst for the C8QI00042E.
hydrogen evolution reaction (HER) in PEM water electrolysis, Int. J. Ionics 24 [110] M.J. Escudero, E. Hontanon, S. Schwartz, M. Boutonnet, L. Daza, Development
(2018) 3113–3121. and performance characterisation of new electrocatalysts for PEMFC, J. Power
[83] P. Millet, N. Mbemba, S.A. Grigoriev, V.N. Fateev, A. Aukauloo, C. Etievant, Sources 106 (2002) 206–214.
Electrochemical performances of PEM water electrolysis cells and [111] S.A. Grigoriev, P. Millet, V.N. Fateev, Evaluation of carbon-supported Pt and
perspectives, Int. J. Hydrogen Energy 36 (2011) 4134–4142. Pd nanoparticles for the hydrogen evolution reaction in PEM water
[84] O.F. Selamet, B. Fatih, D.M. Mahmut, Y. Kaplan, Development and testing of a electrolysers, J. Power Sources 177 (2008) 281–285.
highly efficient proton exchange membrane (PEM) electrolyzer stack, Int. J. [112] P. Millet, D. Dragoe, S. Grigoriev, V. Fateev, C. Etievant, GenHyPEM: a research
Hydrogen Energy 36 (2011) 11480–11487. program on PEM water electrolysis supported by the European commission,
[85] Y. Yin, X. Wang, J. Zhang, X. Shangguan, Y. Qin, Influence of sloping baffle Int. J. Hydrogen Energy 34 (2009) 4974–4982.
plates on the mass transport and performance of PEMFC, Int. J. Energy Res. [113] S.A. Grigoriev, M.S. Mamat, K.A. Dzhus, G.S. Walker, P. Millet, Platinum and
(2018) 1–13. palladium nano-particles supported by graphitic nano-fibers as catalysts for
[86] S. Jakub Mali, R. Petr Mazu, M. Paidar, T. Bystron, K. Bouzek, Nafion117 PEM water electrolysis, Int. J. Hydrogen Energy 36 (2011) 4143–4147.
stability under conditions of PEM water electrolysis at elevated temperature [114] J. Wua, Z. Yanga, Q. Sunb, X. Li, P. Strasserd, R. Yanga, Synthesis and
and pressure, Int. J. Hydrogen Energy 41 (2016) 2177–2188. electrocatalytic activity of phosphorus-doped carbon xerogel for oxygen
[87] P. Millet, S.A. Grigoriev, V.I. Porembskiy, Development and characterisation of reduction, Electrochim. Acta 127 (2014) 53–60.
a pressurized PEM bi-stack electrolyser, Int. J. Energy Res. 37 (2012) 449–456. [115] Z. Liu, Q. Shi, R. Zhang, Q. Wang, G. Kang, F. Peng, Phosphorus doped carbon
[88] P. Lettenmeier, R. Wang, R. Abouatallah, B. Saruhan, O. Freitag, P. Gazdzicki, T. nanotubes supported low Pt loading catalyst for the oxygen reduction
Morawietz, R. Hiesgen, A.S. Gago, K.A. Friedrich, Low-cost and durable bipolar reaction in acidic fuel cells, J Power Sources 268 (2014) 171–175.
plates for proton exchange membrane electrolyzers, Sci. Rep. 7 (2017) 44035. [116] M. Terrones, P.M. Ajayan, F. Banhart, X. Blase, D.L. Carroll, J.C. Charlier, et al.,
[89] S. Lædre, O. Edvard Kongstein, A. Oedegaard, H. Karoliussen, F. Seland, N-doping and coalescence of carbon nanotubes: synthesis and electronic
Materials for proton exchange membrane water electrolyzer bipolar plates, properties, Appl. Phys. A 74 (2002) 355–361.
Int. J. Hydrogen Energy 42 (2017) 2713–2723. [117] T.-J. Li, M.-H. Yeh, W.-H. Chiang, Y.-S. Li, G.-L. Chen, Y.-A. Leu, T.-C. Tien, S.-C.
[90] P. Millet, R. Ngameni, S.A. Grigoriev, V.N. Fateev, Scientific and engineering Lo, L.-Y. Lin, J.-J. Lin, K.-C. Ho, Boron-doped carbon nanotubes as metal-free
issues related to PEM technology: water electrolysers, fuel cells and unitized electrocatalyst for dyesensitized solar cells: heteroatom doping level effect
regenerative systems, Int. J. Hydrogen Energy 36 (2011) 4156–4163. on tri-iodide reduction reaction, J. Power Sources 375 (2018) 29–36.
[91] A.S. Gago, S.A. Ansar, B. Saruhan, U. Schulz, P. Lettenmeier, N.A. Canas, P. [118] Y. Zhou, M. Ruguang, S.L. Candelaria, J. Wang, Q. Liu Evan Uchaker, P. Li, Y.
Gazdzicki, T. Morawietz, R. Hiesgen, J. Arnold, K.A. Friedrich, Protective Chen, G. Cao, Phosphorus/sulfur Co-doped porous carbon with enhanced
coatings on stainless steel bipolar plates for proton exchange membrane specific capacitance for supercapacitor and improved catalytic activity for
(PEM) electrolysers, J. Power Sources 307 (2016) 815–825. oxygen reduction reaction, J. Power Sources 314 (2016) 39–48.
[92] J. Moreira, P. del Angel, A.L. Ocampo, P.J. Sebastian, J.A. Montoya, R.H. [119] J.M. Hu, H.M. Meng, J.Q. Zhang, C.N. Cao, Degradation mechanism of long
Castellanos, Synthesis, characterization and application of a Pd/Vulcan and service life Ti/IrO2-Ta2O5 oxide anodes in sulphuric acid, Corros. Sci. 44
Pd/C catalyst in a PEM fuel cell, Int. J. Hydrogen Energy 29 (2004) 915–920. (2002) 1655–1668.
[93] M.T. Giacomini, M. Balasubramanian, S. Khalid, J. McBreen, E.A. Ticianelli, [120] S. Shiva Kumar, S.U.B. Ramakrishna, B. Rama Devi, V. Himabindu,
Characterization of the activity of palladium-modified polythiophene Phosphorus-doped graphene supported palladium (Pd/PG) electrocatalyst
electrodes for the hydrogen oxidation and oxygen reduction reactions, J. for the hydrogen evolution reaction in PEM water electrolysis, Int. J. Green
Electrochem. Soc. 150 (2003) A588–A593. Energy 15 (2018) 558–567.
[94] C. Rozain, E. Mayousse, N. Guillet, P. Millet, Influence of iridium oxide [121] W.-F. Chen et al., Highly active and durable nanostructured molybdenum
loadings on the performance of PEM waterelectrolysis cells: part I-Pure IrO2- carbide electrocatalysts for hydrogen production, Energy Environ. Sci. 6
based anodes, Appl. Catal., B 182 (2016) 153–160. (2013) 943–951.
[95] C. Rozain, E. Mayousse, N. Guillet, P. Millet, Influence of iridium oxide [122] L. Fan et al., Atomically isolated nickel species anchored on graphitized
loadings on the performance of PEM waterelectrolysis cells: Part II – carbon for efficient hydrogen evolution electrocatalysis, Nat. Commun. 7
advanced oxygen electrodes, Appl. Catal., B 182 (2016) 153–160. (2016) 10667.
[96] L. Yin, T. Yang, X. Ding, M. He, W. Wei, T.T. Yu, H. Zhao, Synthesis of [123] D.-Y. Wang et al., Highly active and stable hybrid catalyst of cobalt-doped
phosphorus-iridium nanocrystals and their superior electrocatalytic activity FeS2 nanosheets– carbon nanotubes for hydrogen evolution reaction, J. Am.
for oxygen evolution reaction, Elecom (2018), 16 August 2018. Chem. Soc. 137 (2015) 1587–1592.
[124] B. Barman Kumar, K.K. Nanda, CoFe nanoalloys encapsulated in N-doped towards the oxygen evolution reaction and stability in acidic media,
graphene layers as Pt-free multi-functional robust catalyst: elucidating the ChemElectroChem 2 (2015) 1128–1137.
role of Co-alloying and N-doping, ACS Sustainable Chem. Eng. 6 (2018) [151] M.K. Datta, K. Karan, O.I. Velikokhatnyi, H.J. Prashanth, S.J. Chung, A.P. James,
12736–12745. A. Manivannan, N.K. Prashant, High performance robust F-doped tin oxide
[125] R. Wu et al., Metallic WO2–carbon mesoporous nanowires as highly efficient based oxygen evolution electro-catalysts for PEM based water electrolysis, J.
electrocatalysts for hydrogen evolution reaction, J. Am. Chem. Soc. 137 Mater. Chem. A 1 (2013) 4026–4037.
(2015) 6983–6986. [152] G. Shrinath Dattatray, P. Prasad Patel, M.K. Datta, O.I. Velikokhatnyi, M.
[126] Y. Pan et al., Carbon nanotubes decorated with nickel phosphide Pavithra Shanthi, N.K. Prashant, First report of vertically aligned (Sn, Ir)O2: F
nanoparticles as efficient nanohybrid electrocatalysts for the hydrogen solid solution nanotubes: highly efficient and robust oxygen evolution
evolution reaction, J. Mater. Chem. A 3 (2015) 13087–13094. electrocatalysts for proton exchange membrane based water electrolysis, J.
[127] S. Trasatti, G. Buzzanca, Ruthenium dioxide – new interesting electrode Power Sources 392 (2018) 139–149.
material – solid state structure and electrochemical behavior, J. Electroanal. [153] S. Anantharaj, S.R. Ede, K. Karthick, S. Sam Sankar, K. Sangeetha, P.E. Karthik,
Chem. 29 (1971) A1. Subrata Kundu, Precision and correctness in the evaluation of electrocatalytic
[128] X. Sun, K. Xu, C. Fleischer, X. Liu, M. Grandcolas, R. Strandbakke, T.S. Bjørheim, water splitting: revisiting activity parameters with a critical assessment,
T. Norby, A. Chatzitakis, Earth-abundant electrocatalysts in proton exchange Energy Environ. Sci. 4 (2018) 744–771.
membrane electrolyzers, Catalysts 8 (2018) 657. [154] A.T. Marshall, S. Sunde, M. Tsypkin, R. Tunold, Performance of a PEM water
[129] S. Cherevko, Stability and dissolution of electrocatalysts: Building the bridge electrolysis cell using IrxRuyTazO2 electrocatalysts for the oxygen evolution
between model and ‘‘real world” systems, Curr. Opin. Electrochem. 8 (2018) electrode, Int. J. Hydrogen Energy 32 (2007) 2320–2324.
118–125. [155] J.Y. Lim, G. Rahman, S.Y. Chae, K.-Y. Lee, C.-S. Kim, O.-S. Joo, Highly stable
[130] Mayousse, Maillard, Fouda-Onana, Sicardy, Guillet, Synthesis and RuO2/SnO2 nanocomposites as anode electrocatalysts in a PEM water
characterization of electrocatalysts for the oxygen evolution in PEM water electrolysis cell, Int. J. Energy Res. 37 (2013) 875–883.
electrolysis, Int. J. Hydrogen Energy 36 (2011) 10474–10481. [156] S.A. Grigoriev, P. Millet, S.V. Korobtsev, V.I. Porembskiy, M. Pepic, C. Etievant,
[131] S. Siracusanoa, N. Van Dijk, E. Payne-Johnsonb, V. Baglioa, A.S. Aricò, et al., Hydrogen safety aspects related to high-pressure polymer electrolyte
Nanosized IrOx and IrRuOx electrocatalysts for the O2 evolution reaction in membrane water electrolysis, Int. J. Hydrogen Energy 34 (2009) 5986–5991.
PEM water electrolysers, Appl. Catal., B 164 (2015) 488–495. [157] Y. Zhang, C. Wang, N. Wan, Z. Liu, Z. Mao, Study on a novel manufacturing
[132] G. Li et al., Zeolite-templated IrxRu1 xO2 electrocatalysts for oxygen process of membrane electrode assemblies for solid polymer electrolyte
evolution reaction in solid polymer electrolyte water electrolyzers, Int. J. water electrolysis, Electrochem. Com. 9 (2007) 667–670.
Hydrogen Energy 37 (2012) 16786–16794. [158] H.C. Ma, C.P. Liu, J.H. Liao, Y. Su, X.Z. Xue, W. Xing, Study of ruthenium oxide
[133] M. Kalliopi Papazisi, A. Siokou, S. Balomenou, D. Tsiplakides, Preparation and catalyst for electrocatalytic performance in oxygen evolution, J. Mol. Catal. A:
characterization of IrxPt1-xO2 anode electrocatalysts for the oxygen evolution Chem. 247 (2006) 7–13.
reaction, Int. J. Hydrogen Energy 37 (2012) 16642–16648. [159] J. Cheng, H. Zhang, G. Chen, Y. Zhang, Study of Ir(x)Ru(1–x)O(2) oxides as anodic
[134] M. Morimitsu, R. Otogawa, M. Matsunaga, Effects of cathodizing on the electrocatalysts for solid polymer electrolyte water electrolysis, Electrochim.
morphology and composition IrO2-Ta2O5/Ti anodes, Electrochim. Acta 46 Acta 54 (2009) 6250–6256.
(2000) 401–406. [160] S.D. Song, H.M. Zhang, X.P. Ma, Z.G. Shao, R.T. Baker, B.L. Yi, Electrochemical
[135] A. De Oliveira-Sousa, M.A.S. Da Silva, S.A.S. Machado, L.A. Avaca, P. De, Lima- investigation of electrocatalysts for the oxygen evolution reaction in PEM
Neto, Influence of the preparation method on the morphological and water electrolyzers, Int. J. Hydrogen Energy 33 (2008) 4955–4961.
electrochemical properties of Ti/IrO2-coated electrodes, Electrochim. Acta [161] L.D. Burke, A. Moynihan, Oxygen electrode reaction. Part 1. Nature of
45 (2000) 4467–4473. inhibition process, Trans. Faraday Soc. 67 (1971) 3550–3557.
[136] H. Chuanpu, L. Hong, M. Cangen, Y. Song, J. Ma, Investigation of mesoporous [162] J. Xu, R. Miao, T. Zhao, J. Wu, X. Wang, A novel catalyst layer with hydrophilic-
niobium-doped TiO2 as an oxygen evolution catalyst support in an SPE water hydropholbic meshwork and pore structure for solid polymer electrolyte
electrolyzer, ACS Sustainable Chem. Eng. 4 (2016) 746–756. water electrolysis, Electrochem. Commun. 13 (2011) 437–439.
[137] M. Petr, P. Jakub, P. Martin, B. Karel, Non-conductive TiO2 as the anode [163] S. Shiva Kumar, S.U.B. Ramakrishna, K. Naga Mahesh, B. Rama Devi, V.
catalyst support for PEM water electrolysis, Int. J. Hydrogen Energy 37 (2012) Himabindu, Palladium supported on phosphorus–nitrogen dual doped
12081–12088. carbon nanoparticles as cathode for hydrogen evolution in PEM water
[138] H.K. Ju, S. Giddey, P.S. Sukhvinder, Badwal, The role of nanosized SnO2 in Pt- electrolyser, Ionics (2018), Accepted, 30-10-2018.
based electrocatalysts for hydrogen production in methanol assisted water [164] S. Shiva Kumar, S.U.B. Ramakrishna, D. Bhagawan, V. Himabindu, Preparation
electrolysis, Electrochim. Acta 229 (2017) 39–47. of RuxPd1-xO2 electrocatalysts for the oxygen evolution reaction (OER) in PEM
[139] L.A. De Faria, J.F.C. Boodts, S. Trasatti, Electroanalytical properties of ternary water electrolysis, Ionics 24 (2018) 2411–2419.
oxide mixtures of composition Ru0.3Ti(0.7-x)CexO2: oxygen evolution from [165] T. Audichon, E. Mayousse, S. Morisset, C. Morais, C. Comminges, W. Teko, K.
acidic solution, J. Appl. Electrochem. 26 (1996) 1195–1199. Napporn, Boniface Kokoh, Electroactivity of RuO2-IrO2 mixed nanocatalysts
[140] A.J. Terezo, J. Bisquert, E.C. Pereira, G. Garcia-Belmonte, Separation of toward the oxygen evolution reaction in a water electrolyzer supplied by a
transport, charge storage and reaction processes of porous electrocatalytic solar profile, Int. J. Hydrogen Energy 39 (2014) 16785–16796.
IrO2 and IrO2/Nb2O5 electrodes, J. Electroanal. Chem. 508 (2001) 59–69. [166] I. Fırtına, S. Guner, A. Albostan, Preparation and characterization of
[141] G. Chen, X. Chen, P. Yue, Electrochemical behavior of novel Ti/IrOx-Sb2O-SnO2 membrane electrode assembly (MEA) for PEMFC, Int. J. Energy Res. 35
anodes, J. Phys. Chem. B 106 (2002) 4364–4369. (2011) 146–152.
[142] J.-W. Yu, G.-B. Jung, Y.-J. Su, C.-C. Yeh, M.-Y. Kan, C.-Y. Lee, C.-J. Lai, Proton [167] C. Immerz, M. Paidar, G. Papakonstantinou, B. Bensmann, T. Bystron, T.
exchange membrane water electrolysis system-membrane electrode Vidakovic-Koch, K. Bouzek, K. Sundmacher, R. Hanke-Rauschenbach, Effect of
assembly with additive, Int. J. Hydrogen Energy (2018), Accepted 22 the MEA design on the performance of PEMWE single cells with different
November. sizes, J. Appl. Electrochem. 48 (2018) 701–711.
[143] R. Ma, S. Cheng, X. Zhang, S. Li, Z. Liu, X. Li, Oxygen evolution and corrosion [168] S.A. Grigoriev, P. Millet, S.A. Volobuev, V.N. Fateev, Optimization of porous
behavior of low-MnO2-content Pb-MnO2 composite anodes for metal electro current collectors for PEM water electrolysers, Int. J. Hydrogen Energy 34
winning, Hydrometallurgy 159 (2016) 6–11. (2009) 4968–4973.
[144] S. Themsirimongko, N. Promsawan, S. Saipanya, Noble metal and Mn3O4 [169] J.O. Majasan, J.I.S. Cho, I. Dedigama, D. Tsaoulidis, P. Shearing, D.J.L. Brett,
supported carbon nanotubes: enhanced catalysts for ethanol Two-phase flow behaviour and performance of polymer electrolyte
electrooxidation, Int. J. Electrochem. Sci. 11 (2016) 967–982. membrane electrolysers: electrochemical and optical characterization, Int.
[145] J.L. Corona-Guinto, L. Cardeno-Garcıa, D.C. Martınez-Casillas, J.M. Sandoval- J. Hydrogen Energy 43 (2018) 15659–15672.
Pineda, P. Tamayo-Meza, R. Silva-Casarin, R.G. Gonzalez-Huerta, Performance [170] A. Kadier, Y. Simayi, P. Abdeshahian, N. Farhana Azman, K. Chandrasekhar,
of a PEM electrolyzer using RuIrCoOx electrocatalysts for the oxygen Md. Sahaid Kalil, A comprehensive review of microbial electrolysis cells
evolution electrode, Int. J. Hydrogen Energy 38 (2013) 12667–12673. (MEC) reactor designs and configurations for sustainable hydrogen gas
[146] P. Vinod Kumar, P. Sivakumar, H. Su, X. Liu, B. Pollet, Keith Scott, Investigation production, Alexandria Eng. J. 55 (2016) 427–443.
of supported IrO2 as electrocatalyst for the oxygen evolution reaction in [171] H. Liu, S. Grot, B.E. Logan, Electrochemically assisted microbial production of
proton exchange membrane water electrolyser, Int. J. Hydrogen Energy 39 hydrogen from acetate, Environ. Sci. Technol. 39 (2005) 4317–4320.
(2014) 1905–1913. [172] N.K. Rathinam, R.K. Sani, D. Salem, Rewiring extremophilic electrocatalytic
[147] K. Karan, M.K. Datta, I. Oleg Velikokhatnyi, H.J. Prashanth, N.K. Prashanth, processes for production of biofuels and value-added compounds from
Fluorine doped (Ir, Sn, Nb)O2 anode electro-catalyst for oxygen evolution via lignocellulosic biomass, in: R. Sani, N. Krishnaraj Rathinam (Eds.),
PEM based water electrolysis, Int. J. Hydrogen Energy 39 (2014) 664–674. Extremophilic Microbial Processing of Lignocellulosic Feedstocks to
[148] P. Vinod Kumar, P. Sivakumar, S. Basu, Xu. Wua, Su. Huaneng, N. Biofuels, Value-Added Products, and Usable Power, Springer, Cham, 2018,
Varagunapandiyan, B. Pollet, K. Scott, RuxNb1-xO2 catalyst for the oxygen pp. 229–245.
evolution reaction in proton exchange membrane water electrolysers, Int. J. [173] A. Kadier, Md. Sahaid Kalil, P. Abdeshahian, K. Chandrasekhar, A. Mohamed,
Hydrogen Energy 38 (2013) 8605–8616. N. Farhana Azman, W. Logroño, Y. Simayi, A. Abdul Hamid, Recent advances
[149] S. Ardizzone, C. Bianchi, G. Cappelletti, M. Ionita, A. Minguzzi, S. Rondinini, and emerging challenges in microbial electrolysis cells (MECs) for microbial
Composite ternary SnO2/IrO2/Ta2O5 oxide electrocatalysts, J. Electroanal. production of hydrogen and value-added chemicals, Renewable Sustainable
Chem. 589 (2006) 160–166. Energy Rev. 61 (2016) 501–525.
[150] T. Audichon, S. Morisset, T.W. Napporn, K. Boniface Kokoh, C. Comminges, C.
Morais, Effect of adding CeO2 to RuO2–IrO2 mixed nanocatalysts: activity

Hydrogen Production by PEM Water Electrolysis - A Review

Uploaded by

Copyright:

Available Formats

Hydrogen Production by PEM Water Electrolysis - A Review

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Hydrogen Production by PEM Water Electrolysis - A Review

Uploaded by

Copyright:

Available Formats

Materials Science for Energy Technologies 2 (2019) 442–454

Contents lists available at ScienceDirect

Materials Science for Energy Technologies

Hydrogen production by PEM water electrolysis – A review

Production and hosting by Elsevier

1. Introduction gasses [31–33]. Further, the unremittingly growing the global

Fig. 1. Various Hydrogen Production Methods.

Hydrogen Advantages Disadvantages Efficiency Cost [$/kg]

2. Water electrolysis technologies mechanism as shown in Fig. 2. Alkaline electrolysis operates at

3. Alkaline water electrolysis (AWE)

Hydrogen production by alkaline water electrolysis is well

[37,50]. Finally, a new approach in the alkaline electrolysis is under

4. Solid oxide electrolysis (SOE)

The solid oxide electrolysis (SOE) first introduced by Donitz and

6. PEM water electrolysis

The first PEM water electrolysis was idealized by Grubb in the

high-pressure operations. In terms of sustainability and environ-

6.1. Principle of PEM water electrolysis

In PEM water electrolysis, water is electrochemically split into

Electrolysis process Advantages Disadvantages

6.3. Faradaic efficiency 6.4. PEM water electrolysis cell components

Supplementary data to this article can be found online at

In this review, we have discussed a short introduction about the References

You might also like