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The Role of Electrocatalysts in the Development of Gigawatt-Scale

PEM Electrolyzers
Ryan J. Ouimet, Jennifer R. Glenn, Diana De Porcellinis, Andrew R. Motz, Marcelo Carmo,
and Katherine E. Ayers*

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ABSTRACT: Electrocatalysts are nanomaterials of paramount importance within water electrolyzers, because they facilitate the
Downloaded via UNIV DEL VALLE on February 23, 2023 at 17:18:54 (UTC).

electron transfer between reactants and electrode, enabling the chemical transformation of water into hydrogen and oxygen. In this
Perspective, recent findings in electrocatalyst development for the next generation of polymer electrolyte membrane (PEM) water
electrolyzers at scale are discussed. We discuss opportunities to create catalyst architectures, the importance to demonstrate
electrode manufacturing tools, and how useful advanced characterization methods shall, in the short term, allow large-scale
deployment of water splitting devices with higher efficiency, acceptable durability, and low cost. We envision next-generation PEM
cells permitting a transformational change in the chemical industry by the manufacturing of low-cost hydrogen.

1. INTRODUCTION As the cost of renewable electricity decreases, the economics of

Green Hydrogen. In recent years, many governments green hydrogen produced by water electrolysis has greatly
worldwide have begun to focus on developing hydrogen as part improved and, in some locations, is now comparable to
of a clean energy future. In June 2019, only two countries had hydrogen produced from methane (called “blue hydrogen”).5
Alkaline Water Electrolyzers. Using renewable energy to
published hydrogen strategies, while as of November 2021, 17
power electrolyzers has been a commercial practice since the
governments have published strategies, with more than 20
1900s. Alkaline electrolyzers were coupled to hydroelectric
additional countries developing strategies.1 Hydrogen has been
power to produce hydrogen for ammonia generation.4 Over
identified as a fuel of high propositional value that can be used
400 electrolyzers were in operation by 19006 and further
for a wide variety of applications across many industrial sectors
development of alkaline electrolyzer technology led to the
and plays a crucial role to reduce greenhouse gas emissions.
deployment of systems at the megawatt scale (see Figure 1)
Most countries that have developed hydrogen strategies have
that well represent today’s maturity and reliability.4 Tradition-
focused on the increased use of hydrogen in the transportation
ally, alkaline electrolyzer stacks have operated at low current
and industry sectors. With the transportation sector resulting
density, such that to meet the hydrogen demand, multiple
in 27% of the global greenhouse gas emissions, there has been
electrolyzer stacks with a large footprint must be deployed.
a greater shift toward using hydrogen as a fuel for
These characteristics are described solely to discuss the history
transportation such as fuel cell electric vehicles (FCEVs).
of electrolysis and to provide a baseline to compare to polymer
Between 2017 and 2021, there has been a 600% sales increase
electrolyte membrane water electrolyzers.
in FCEVs.1 Across industry, hydrogen can also be used in the
Polymer Electrolyte Membrane Water Electrolyzers
development of chemicals and fertilizers,2 as well as the
(PEMWEs). Polymer electrolyte membrane water electrolyzers
production of carbon-free steel.3 Other applications of
(PEMWEs), as shown in Figures 1 and 2,8 have been under
hydrogen include the energy storage and stabilization of the
development since 1955.4 PEM cells use electrodes that have
electric grid.
been deposited onto a solid polymer electrolyte membrane
Unfortunately, 96% of today’s hydrogen is still generated
made of perfluorosulfonic acids (PFSAs), which allows for the
using natural gas reforming and coal gasification.4 Despite the
transport of protons across it and optimized ionic resistance
global demand of hydrogen in 2020 being 90 Mt, the use of
across the PFSA. The improved performance allows for PEM
fossil fuels as the source of hydrogen has led to 900 Mt of CO2
stacks to operate at high current densities and allows for a
emissions.1
Hydrogen via Water Electrolyzers. An alternative and
yet sustainable method for hydrogen production is via water Received: February 1, 2022
electrolyzers coupled to renewable energy sources such as Published: May 9, 2022
wind, solar, tidal, etc.: the so-called “green hydrogen”.
Unfortunately, high electricity costs have hampered the
economics of green hydrogen and prevented the widespread
use of electrolyzer technology for energy storage applications.

© 2022 American Chemical Society https://doi.org/10.1021/acscatal.2c00570

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Figure 1. Different multi-megawatt-scale polymer electrolyte
membrane water electrolyzers (PEMWEs) at NEL Hydrogen.
Figure 2. Schematic diagrams of PEMWEs.
significantly reduced footprint, when compared with alkaline
technology. Moreover, commercial PEM water electrolyzers
have been able to demonstrate high reliability with a reported
>60 000 h of operation,7 and many other units from NEL
Hydrogen with fielded lifetimes of over 7−10 years.
Despite its wide window of power operating range, high
reliability, and compact stack/system design demonstrated by
PEMWEs, challenges still exist. Polymer electrolyte membrane
(PEM) components require expensive platinum group metal
(PGM) catalysts, titanium-based components, and significantly
expensive PFSA membranes. Historically, iridium-based
catalysts have been used as the anode catalyst. Because of
the slow reaction kinetics associated with the oxygen evolution
reaction at the anode, a significant amount of iridium (1−3
mgIr/cm2) is used in electrode manufacturing to allow for
acceptable cell performance4 and robustness. Similarly,
platinum has been used as the cathode catalyst.
Gigawatt-Scale PEM Water Electrolyzers. As of 2019,
the large share of PEM water electrolyzer systems were
operating at the 50−200 kW scale.4 Only recently have larger
systems on the megawatt scale been deployed. In 2021, Nel
partnered with Iberdrola to deploy a 20 MW PEM system that
will be used to produce green fertilizer and is, today, among
the largest installed PEM systems in the world.9 Other projects
on the hundreds of megawatts scale are currently being
planned.1 Despite recent megawatt-scale PEM installations, the
demand for green hydrogen, for instance within the steel
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industry, is still far greater than the supply. As of 2021, there
are ∼350 electrolysis projects being developed that could
increase the installed capacity from current 0.3 GW to 54 GW
while an additional 40 projects are in the planning stage that
could further increase that capacity to 89 GW.1 While the
current electrolysis capacity may increase 179-fold with the
currently planned projects, this still falls far below the
electrolysis demand required for the IEA’s “Net Zero
Emissions by 2050 Scenario”. According to the IEA, installed
electrolysis capacity must increase from the current 0.3 GW to
850 GW by 2030 and 3600 GW by 2050.1
To develop gigawatt-scale PEM water electrolyzers, many
challenges must be addressed. We will review current activities
to reduce catalyst loading as well as the challenges associated
with the use of lesser amounts of PGM catalysts. We will also
examine the development of novel catalysts that can be used to
further reduce the need to use PGM catalysts and list the
challenges associated with catalyst characterization methods
that are currently being used. The paper will conclude with a
market outlook on material availability and additional methods
that can be used for reducing the costs of electrodes.
2. REQUIREMENTS AND OPPORTUNITIES WITH
REDUCED IRIDIUM CATALYST LOADING
Priority of Reduced Iridium Loading. Iridium-based
catalysts have proven to be the most durable high-performance
oxygen evolution reaction (OER) catalysts for PEM water
electrolysis and, to date, the only commercially viable option.
Iridium is scarce and expensive; therefore, low iridium loading
has been receiving increased attention by the research and
development (R&D) community and academia. Consider-
ations for the impact on H2 cost are paramount for ensuring
the research community is putting proper emphasis on
catalysts alternatives that can become commercially viable. A
cost sensitivity analysis was performed using high PGM cost
based on the maximum Engelhard Industrial Bullion spot price
over the last 10 years. Specifically, the values used were
$48.22/g for Pt and $205.76/g for Ir. The sensitivity of H2 cost
was analyzed for changes to stack life, voltage efficiency,
platinum loading, and iridium loading (see Figure 3). The data
support that, today, maintaining (or improving) stack lifetime
and voltage efficiency are higher priority than reducing the
PGM content, from a cost perspective alone.
There are some obvious cost benefits to reducing the PGM
loading. A less-noted benefit of going to lower PGM loadings is
the added stability in H2 cost, despite the volatile PGM market.
Two additional scenarios were analyzed to demonstrate this
benefit. A low PGM loading scenario (0.25 mg Ir/cm2 and 0.05
mg Pt/cm2) and a high PGM scenario (3.0 mg Ir/cm2 and 1.0
mg Pt/cm2) can be seen in Figure 4. The main conclusion
from this analysis is that stack lifetime and voltage efficiency
are still critical to the overall cost of H2 in both scenarios, but
at high PGM loadings, the iridium cost fluctuations also play a
significant role, which would be more apparent when looking
at the impact on Capex alone.
Another important motivation for reducing PGM loading is
scarcity, primarily for iridium. The global annual iridium
production is ∼5.0−7.7 t.10 However, to date, there is no
specific market that draws higher mining rates, and iridium is
still a subproduct of platinum extracting. Taking 10% of the
annual production (7−8 tons)10 and the status quo, high
iridium loadings (2.0 mg Ir/cm2) combined with typical
operating conditions (2 A/cm2 and 2 V) results in a total of >1
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Figure 3. Tornado plot showing the sensitivity of total H2 cost
(CapEx and OpEx included) with variations in stack lifetime, voltage
efficiency, platinum loading, and iridium loading. This assumes a high
PGM cost set to the highest spot price over the last 10 years. Bars
represent changes in cost, compared to the nominal case for each
perturbation as listed on the left.
GW per year PEMWE production capacity. As the global
production of PEMs increases beyond 1 GW/yr, iridium will
need to be used in a more efficient manner to avoid an iridium
shortage.10 It is from this analysis that we conclude a key
enabler for a multi-GW per year PEMWE market is reducing
iridium usage, with the caveat that performance and durability
must not be sacrificed.
Challenges with Reduced Iridium Loading. Lowering
catalyst loading is typically understood to have a direct, rapid,
and detrimental effect over stack voltage degradation. An
example of this is a recent article by Alia et al., where the
interplay between iridium loading and voltage profile was
reported, with respect to durability.11 Figure 5 clearly shows
the decrease in current density after long-term studies using
low-loaded electrodes.11
As PEM electrolyzers are increasingly deployed and coupled
with renewable energy, they will have added stressors due to
voltage cycling. Some initial progress has been made recently
to understand the fundamental reasons for lower performance
and durability with low loaded electrodes. One key aspect
impacting the performance is the interface with the adjacent
porous transport layer (PTL). In a study by Gasteiger et al., the
performance of a low iridium loaded cell was shown to
improve when the interfacing component had more uniform
Figure 4. Tornado plot showing the sensitivity of total H2 cost (CapEx and OpEx included) with variations in stack lifetime, voltage efficiency,
platinum cost, and iridium cost. Low PGM loading of 0.25 mg Ir/cm2 and 0.05 mg Pt/cm2 (left); and high PGM loading sensitivity analysis of 3.0
mg Ir/cm2 and 1.0 mg Pt/cm2 (right). Bars represent changes in cost, compared to the nominal case for each perturbation as listed on the left.
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contact provided by a carbon layer with an MPL.12 The
hypothesis is that the electronic transport in the catalyst layer
is inhibited due to the overall thickness and discontinuities. Liu
et al. also show the importance of a continuous and well
conductive PTL/catalyst layer interface, showing that non-
coated PTLs will trigger delamination of the catalyst layer after
a 4000 h test (see Figure 6).13
Another method to achieve acceptable performance with
low loaded electrodes is to move to a supported catalyst where
the electronic conductivity and the iridium packing density
were concluded to be two key parameters.14 Alternative
approaches to reduce catalyst loading while maintaining
durability include utilizing 1D and 2D nanomaterials. One
specific example is a study where low loaded electrodes with
nanorods, nanoparticles, and a mixture of nanorods and
nanoparticles were tested. The results show that the perform-
ance of the mixed electrode improves, in contrast to either of
the electrodes with only a single component.15 One
explanation for these results is the improved, in-plane
electronic conductivity enabled by the nanorods in con-
junction with the high surface area from the nanoparticles.
Another approach was taken by Danilovic and co-workers,
where nanosheets were used to demonstrate loadings as low as
0.06 mg Ir/cm2 that was stable over 50 000 voltage cycles.16
An alternative approach used to fabricate low loaded electrodes
for PEMWE is the reactive spray deposition technology
(RSDT) process17.18 Yu et al. were able to use the RSDT
process to develop catalyst-coated membranes (CCMs) that
operated for over 4500 h of operation with an anode electrode
that had a loading of 0.08 mg Ir/cm2.18 The high performance
demonstrated by the RSDT CCMs has been attributed to a
high ratio of Ir(IV) to Ir(III) in the RSDT-synthesized IrOx
nanoparticles, as well as a uniform electrode structure.
Key opportunities exist in reducing iridium loadings through
improved interfaces, extended catalyst structures (1D and 2D
nanomaterials), and using oxidatively stable support structures.
In addition to understanding the initial performance
comparison to baseline loadings, it is important to understand
the durability implications of lower catalyst loading.
3. CHALLENGES WITH BALANCING ACTIVITY AND
STABILITY OF OXYGEN EVOLUTION REACTION
CATALYSTS
The activity of PGM catalysts for water splitting have been
previously examined based on the volcano plot developed by
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Figure 5. Square wave voltage cycling between 1.45 V and the upper voltage as listed in the x-axis. The y-axis is the current at 2.0 V, and the color
represents the number of total cycles: (a) 0.40 mg Ir/cm2, (b) 0.20 mg Ir/cm2, and (c) 0.10 mg Ir/cm2. Reproduced from reference 11.

Figure 6. Importance of the PTL/catalyst layer interface, showing that noncoated PTLs will trigger delamination of the catalyst layer after a 4000-h
test. Reproduced from reference 13.

Trasatti in 1984.19 Figure 7 shows that ruthenium oxide is
more active than iridium oxide as an OER catalyst. Strmcnik et
al. concluded that the OER activity improves because of
increased oxophilicity of the catalyst.20,21 Despite other
elements showing improved performance compared to the
scarce and expensive iridium oxide, many of these catalysts
have a high degradation rate. Danilovic et al. stated that the
stability of the catalyst is inversely proportional to its activity20
(see Figure 7). For example, while operating at a constant
current density of 5 mA/cm2, the authors were able to report
that osmium oxide had the lowest OER overpotential of 0.05 V
(7.6 times lower than that of iridium oxide), yet the highest
dissolution at 20 ppb (333.3 times greater than IrO2).20
Similarly, while ruthenium oxide showed 1.7 times greater
activity when compared to iridium oxide, the dissolution rate
was 80.7 times worse. From these studies, there is an evident
balance that must be taken between utilizing a highly active
catalyst while ensuring its stability.
Kim et al. developed a parameter known as the Activity-
Stability Factor (ASF), which compares the activity and
stability of a catalyst at a constant overpotential.22 By using this
parameter, Kim et al. were able to identify materials that have a
proper balance of catalytic activity with long-term stability. The
authors used this ASF approach to compare an iridium oxide
material developed from polycrystalline iridium to an iridium
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oxide shell on Ir core catalyst that was produced through the
dealloying of Ir25Os75. By increasing the electrochemically
active surface area (ECSA), the activity of the iridium oxide
shell on iridium core catalyst was significantly higher and
resulted in a 30 times improvement in the ASF, when
compared to traditional iridium oxide material. Other
researchers have tried to examine the impact of the catalyst
oxidation state on the activity and stability of the catalyst
materials. Cherevko et al. examined the impact of iridium
oxidation state on the dissolution mechanism of iridium oxide
catalysts.23 Those studies showed that oxygenated Ir(III)
intermediate species formed during the oxygen evolution
reaction were leading to the dissolution of iridium resulting in
lower stability. The proposed dissolution mechanism is shown
in Figure 8. Baik et al. used Adam’s fusion to develop catalysts
that had an IrO2 core with an iridium oxide shell with varying
amounts of iridium oxidation states.24 This study showed that
controlling the oxidation states of Ir on the catalyst surface
allowed controlling the activity and stability of the OER
catalyst. In particular, the Ir(III) catalyst on the shell of the
catalyst was shown to provide higher catalytic activity while the
Ir(IV) core prevented dissolution of the catalyst. Similarly, Lee
et al. developed iridium-based catalysts with a gradient
oxidation state with the O/Ir ratio, decreasing from the shell
to the core of the catalyst.25 Following accelerated stress tests,
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Figure 7. Comparison of stability and activity of different metal oxides
that have been prepared by thermal chemical (TC) or electrochemical
(EC) methods. [Reproduced from ref 20. Copyright 2014, American
Chemical Society, Washington, DC.]
Figure 8. Iridium dissolution mechanism occurring during the oxygen
evolution reaction proposed by Cherevko et al. [Reproduced with
permission from ref 23. Copyright 2016, Elsevier.]
the catalyst with gradient Ir oxidation states was shown to have
improved performance and low dissolution rates, when
compared to state-of-the-art iridium oxide, satisfying the
balance between activity and stability.
4. ADVANTAGES AND CHALLENGES OF
ELECTROCATALYST CHARACTERIZATION
METHODS
Advanced Catalyst Characterization Techniques.
Before incorporating a new catalytic material into an
electrolyzer stack, it is imperative to characterize the material,
whether it is a newly synthesized material or a commercially
available catalyst that possesses unknown properties. Here, we
will discuss five of the common analytical characterization
techniques used to investigate catalytic materials, including X-
ray diffraction (XRD), scanning electron microscopy (SEM)
and its coupling with energy dispersion spectroscopy (EDS),
transmission electron microscopy (TEM), and rotating disk
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electrode (RDE). We also aim to highlight the advantages and
limitations of the methods outlined above.
X-ray Diffraction of Crystalline Catalytic Materials.
XRD is a diverse technique that can be utilized for catalysts in
powder, flat solid, and single-crystalline forms. Here, we will
focus mainly on powder and solid samples as most catalytic
materials are eventually processed into some form of an ink
that is applied to a flat surface for use as an electrode in an
electrolyzer stack.26,27,28 This technique can be used to identify
new materials and assess phase purity, but it can also be used
to determine if the crystallinity of a material is changed due to
the conditions to which it is subjected. Such information can
be highly informative as it provides structural information that
may affect the efficiency of the catalyst. XRD can be used to
track purposefully induced changes to obtain desired results, as
exemplified by the work of Cha et al.30 This work, which is
illustrated in Figure 9, shows how XRD was used to determine
Figure 9. XRD patterns illustrating the structural property changes of
IrOx/Ti4O7. [Reproduced with permission from ref 30. Copyright
2022, Elsevier.]
the physical effects of changing the ratio of IrOx to Ti4O7.30
The XRD data, in conjunction with additional testing, led the
authors to conclude that the layered structure of IrOx was
decreasing as the amount of IrOx around the Ti4O7 support
decreased.
XRD can also be used to calculate the crystallite or grain size
of the materials by utilizing the Scherrer equation.31,32
Rietveld refinement is a technique that is scarcely discussed
in the electrolyzer literature33 but widely used in crystallog-
raphy; it is one pathway to assessing the amounts of each
crystallographic phase present. Rietveld refinement is an entire
pattern fitting process that compares a theoretical diffraction
pattern to an experimentally collected diffraction pattern and
allows for the theoretical pattern and the instrument
parameters to be refined so that the theoretical pattern and
experimentally collected pattern better fit each other.34,35 This
fit is expressed both as a graphical comparison and as statistical
values, which define how well the refined parameters allowed
for resolution between the experimental and theoretical
patterns; Reference 36 demonstrates a good example of how
to report the graphical and statistical data.36
It is also possible to use Rietveld refinement to output a
percentage of how much of each theoretical pattern is being
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used to fit to the experimental data when more than one
crystallographic phase is present, which is an indication of how
much of each phase is present within the sample.35 The caveat
with Rietveld refinement is that it requires high-quality
experimental data, and it is possible to overrefine a parameter;
therefore, it is imperative to report all parameters that are
refined in addition to the statistical and graphical output
whenever using this technique. For those interested in learning
more about Rietveld refinement, Argonne National Lab
provides useful introductory information on their website.37
While XRD is a powerful technique, like many others, it
does have limitations that must be respected to achieve the
best data collections and interpretation. The main limitation of
XRD is that this technique is meant for use with crystalline
materials.26−28 Amorphous materials create peak broadening
and can convolute the XRD pattern of a crystalline material
when present. Another limitation of XRD comes from sample
preparation.26−28 Each technique used for sample preparation
will, in some way, affect the experimentally collected XRD
pattern, including induced preferred orientation or the
introduction of an amorphous material to freeze the sample
in place.26−29 The influence of sample preparation cannot be
fully eliminated and therefore should be known, stated, and
taken into consideration when the data are analyzed.
SEM Microstructure of Catalyst Materials and
Electrode Layers. Scanning electron microscopy (SEM) is
a technique that uses a high-resolution electron microscope to
produce micrographs of a sample’s surface using a focused
beam of electrons.28,38 Figure 10 demonstrates how SEM can
Figure 10. SEM images: (a) top view and (b) cross-section of the
catalyst layer prepared by the ultrasonic-spray method. Pt loading:
0.40 mg cm−2 on Sigracet 10BC GDL, (c) top view and (d) cross-
section of catalyst layer (CL) prepared by the US technique. Pt
loading: 0.15 mg cm−2 on Sigracet 10BC GDL, (e) top view and (f)
cross-section of CL prepared by US. Pt loading is 0.05 mg cm−2 on
Sigracet 10BC GDL, (g) top view and (h) cross-section of catalyst
layer prepared by hand-painting. Pt loading: 0.40 mg cm−2 on Sigracet
34BC GDL. Reproduced from reference 39.
be utilized to compare an electrode’s surface when different
catalyst application methods are utilized, thus exemplifying the
important connection between sample preparation and surface
morphology.39
SEM can also be utilized for failure analysis as it is possible
to observe minute details that will affect the functionality of a
material. One example of this is delamination of electrodes
from a membrane, which can be observed by cross sectioning
the sample or the cracking/tearing of a CCM post-operation
that can be seen in Figures 1140 and 12.41
The main limitation for SEM is that organic samples have a
tendency to degrade under the electron beam, making analysis
difficult and unreliable. This can be worked around by applying
a conductive coating such as gold to the surface of the material.
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Figure 11. SEM micrographs of cross sections of (a) CCM with a
well adhered electrode layer and (b) an electrode layer that is starting
to delaminate. [Reproduced with permission from ref 40. Copyright
2006, Elsevier.]
Figure 12. Morphology of a CCM investigated using SEM to observe
the surface topography. (a) The surface of the CCM displaying a
crack in the electrode layer. (b) Cross-sectional micrograph displaying
how the electrode cracking is penetrating the CCM and the beginning
of a pinhole/tearing of the membrane. [Reproduced with permission
from ref 41. Copyright 2006, IOP Publishing.]
Another limitation of SEM is the size of the sample area. SEM
is useful for examining fine details; however, generalizations of
a much larger sample should only be made when multiple areas
have been examined to ensure that the morphological features
are not a localized phenomenon.
Coupling Energy Dispersive Spectroscopy with SEM.
Energy-dispersive spectroscopy (EDS) is frequently used in
conjunction with SEM, because it can use the electron beam
generated by a SEM at a higher accelerating voltage to
semiquantitatively identify the elements within a sample at a
particular point or area.28,42 EDS mapping will also identify the
elements that are present over the analysis area, but in
addition, it can identify the general location of the elements
within the analysis area and artificially color the micrograph to
provide a visual representation of the elemental distribution.
This mapping can be used for many reasons, including
assessing sample homogeneity or to observe elemental
degradation of a sample, as was the case from previous work
displayed in Figure 13.43
EDS is also limited to which elements can be identified by
this technique. Elements with two or less core electrons are not
appropriate for this type of analysis, because the technique
requires a core electron to be removed and another to take its
place; if there are not enough core electrons to complete this
process, the element cannot be identified. Elements with
extremely short half-lives also would not be appropriate for
EDS analysis, since they would degrade before the analysis
could be completed. Also note that EDS is a semiquantitative
technique, because scattering of the X-rays can lead to
misidentification of elements that have similar X-ray wave-
lengths and materials present in the sample chamber, such as
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Figure 13. (a) Degraded cathode catalyst layer and (b−d) energy-
dispersive X-ray analysis (EDX) mapping of Pt and Ir. [Reproduced
with permission from ref 43. Copyright 2020, Elsevier.]
the sample holder/stub, can also be mistakenly identified due
to scattered electrons.
Transmission Electron Microscopy Characterization
of Electrocatalysts. Transmission electron microscopy
(TEM) is a technique that is complementary to XRD and
SEM/EDS.44−46 The report about catalytic reversibility by Lee
et al.47 exemplifies the multiple functions of TEM. This study
investigated the high and low heat treatment of IrNi
nanoparticles on carbon, in which different heat treatments
were investigated as synthesis routes, which is described here
to emphasize the capabilities of TEM. Through TEM analysis
of the low and high heat-treated samples, it was possible to
observe the distribution and approximate size of the nano-
particles as illustrated in Figures 14a and 14d.47 This work has
taken the usage of TEM one step further in Figures 14c and
Figure 14. Morphological and structural characteristics of the
synthesized IrNi nanoparticles supported on carbon at different
heat-treatment temperatures of 400 and 1000 °C, which are denoted
as IrN/C-LT and IrNi/C-Ht, respectively: (a) TEM and (b, c)
HADDF images of IrNi/C-LT; (d) TEM and (e, f) HADDF images
of IrNi/C-HT. The inserted fast Fourier transform of the IrNi/C-HT
particles show the (111) and (200) planes. Reproduced from
reference 47.
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14f to begin to elucidate the crystal planes of the synthesized
nanoparticles, which has allowed the authors to infer the unit
cell, which was confirmed via XRD.47
The main drawback of TEM is that it works best with very
thin samples, since there is less material through which one
must transmit.44,46 Thus, thicker materials are more likely to
contain more particles that are have a higher probability of
overlapping. This can convolute the data and it will no longer
be possible to draw conclusions such as the general density of a
metal on a support material.
Rotating Disk Electrode (RDE). One common character-
ization technique for analyzing electrocatalysts is rotating disk
electrode (RDE). RDE is an ex-situ catalyst characterization
method that involves applying a catalytic thin film on a
working electrode, which is then submerged in an electrolyte
solution and rotated to account for ohmic and mass transport
resistances.48,49 By performing cyclic voltammetry and linear
sweep voltammetry on the working electrode, catalyst activity
and other kinetic information can be obtained and can be used
for the comparison catalysts for many electrochemical
reactions, such as those within water electrolyzers.
Sheng et al. used RDE to measure the hydrogen evolution
reaction (HER) exchange current density, activity, and
activation energy of polycrystalline Pt and Pt/C catalyst
material in acidic and alkaline media.50 Their findings showed
that the HER kinetics of Pt/C and polycrystalline Pt in acid
had much higher activity, when compared to testing in alkaline
electrolyte. However, Sheng et al. also determined that the Pt/
C and polycrystalline Pt could be modeled with the Nernstian
diffusion overpotential, assuming infinitely fast reaction
kinetics.
Similarly, Durst et al. had used RDE as a method to examine
the HER kinetics of supported catalysts.51 The authors
determined that kinetic parameters could not be determined
using RDE, since the limiting diffusion rate was smaller than
the exchange current density of the catalysts being tested,
which led to incorrect measurements. While RDE was shown
to have challenges for measuring HER kinetic parameters of
highly active Pt catalysts, the sluggish kinetics of the OER
reaction can be measured. Cherevko et al. used RDE to
measure the kinetic activity of metallic ruthenium and iridium,
as well as their oxides.52 The authors were able to examine the
onset potential of the OER with different catalysts by
performing linear sweep voltammograms. While OER activity
and kinetics can be reliably determined using RDE, recent
studies have presented concerns and limitations of RDE in
accurately measuring the catalyst stability. Hartig-Weiss et al.
and Tovini et al. reported that catalyst stability measured using
RDE is much lower than catalyst stability measured in a
PEMWE cell.53,54 They have shown that the primary reason for
the worse stability in RDE is the formation of oxygen bubbles
on the catalyst surface that are not completely removed while
the electrode is rotating. The same work showed that
introducing sonication to the RDE electrochemical cell was
found to remove the oxygen bubbles from the working
electrode surface and improve catalyst stability.
For brevity, this Review has highlighted a few key analysis
techniques for PEMWE electrocatalysts. However, that is not
to say that there are not numerous other techniques that could
be extremely useful, depending on the experiment being
conducted. Therefore, the authors would encourage readers
who are interested in further techniques to use the above
techniques as a starting point and look to more analysis-
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Figure 15. Iridium market prices starting in 2020.
focused reviews and publications for additional techniques
such as X-ray photoelectron and absorption spectroscopy, to
name a few.55−57
5. IRIDIUM MARKET AND RECYCLING
As discussed in the previous cost model analysis (see Figures 3
and 4), the costliest part of the membrane assembly electrode
is the catalyst layer. Since the precious metal catalyst supplies
are limited, lack of access to these materials could hinder the
large-scale gigawatt implementation of PEM electrolyzers. As
alternative chemistries or lower PGM content catalyst
solutions are evaluated, it is important to keep in mind that
a performance and/or durability penalty might become a
fundamental parameter in the cost of balance of plant for
gigawatt-scale electrolyzer factories using such novel solutions.
The current inability of the supply chain industries to
increase the production volumes of key components in a timely
manner represents a significant challenge for scale up. Iridium
oxide demand, for example, has been slowly but steadily
increasing, while its production has been drastically reduced by
several external factors, including major mining-site occur-
rences. One of the most renowned accidents occurred in early
2020 at the South Africa mines owned by Anglo American
Platinum and resulted in the closure of the ACP Phase B unit
for more than 90 days. Consequently, the production and the
sales of PGMs including platinum, palladium, rhodium,
ruthenium, and osmium fell from 3.1−3.3 million ounces to
2.5 million ounces. The overall South African production fell
by 25.8%.58
The restrictions in international trade, as well as the different
lockdown measurements instituted by several countries during
the 2020 pandemic, have generated a scarcity crisis on the
market. In less than 5 months, the iridium price has
skyrocketed from less than $2000 per oz to more than
$6000 per oz, as shown in Figure 15,59 although prices have
started to recover.
This manmade scarcity crisis has shifted the stakeholders’
focus to the limited amount of natural PGM reserves,
highlighting the importance of finding alternative catalyst
chemistries based on nonprecious metals and the necessity for
an environmentally sustainable recycling process.
Several techniques have been explored in the fuel cell
industry for the recycling of catalysts from CCMs. The most
well-known process, to recover the Pt from CCM, includes the
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full combustion of the CCM, and a long and expensive
processing of the ashes, as shown in Figure 16, published by
Valente et al.60
Figure 16. Process stream of Pt recovery through CCM incineration.
[Reproduced with permission from ref 60, Copyright 2018, Javier
Dufour.]
Unfortunately, PFSA is used as the ionomer, hydrofluoric
acid (HF) gases are released in the process, and chemical
compatibility and water management issues may arise from this
process. To minimize the release of HF, the CCM can be
processed in the presence of a calcium salt, so that HF would
be trapped as CaF2, but this step adds additional costs. HF
removal from combustion gases by flowing the gaseous stream
through a sorbent bed made from silicon carbide coated with
activated alumina has been explored as an alternative solution.
Unfortunately, the lifetime of the carbide limits the
applicability of this approach.61 BASF and The Virginia
Polytechnic Institute have also explored microwave combus-
tion. The process was shown to be economically feasible for a
three-layer CCM; however, it was not economical for five-layer
CCMs (including the carbon and titanium gas diffusion
layers).61 An industry guideline for reclamation of metals from
common organic matrices has been formalized by BASF and
showed the ability to recover >98% of PGM. The approach
involved a chemical separation of the anode and the cathode
through delamination, followed by a dissolution of the polymer
in a heated bath, and final filtration. The schematic of the
method is reported in Figure 1762
This method utilizes a lower alkyl alcohol solution with mild
heating to delaminate the CCM. This procedure allows the
recovery of both noble metals and polymer membrane. The
addition of alcohols during the dissolution of the membrane in
water at elevated temperature (150−350 °C) can influence the
yield of the process, as shown in Figure 18.
The polymer cannot be reused to recast a membrane, since
it undergoes scission chain reactions that lower its molecular
weight during the process. A membrane cast from the
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ACS Catalysis pubs.acs.org/acscatalysis
Figure 17. Typical example of a recycling process. Reproduced from
reference 62.
Figure 18. Yield of recovery of Pt from aged CCMs at different
temperatures in an alcohol/water solvent mixture with different
concentrations of alcohols. Reproduced from reference 62.
recovered polymer would exhibit different properties,
compared to the original CCM. Nonetheless, the recovered
polymer can be used for plastic recycling, since no toxic HF
was formed and no combustion was necessary. Since no
emission of HF and carbon dioxide occurred, the only
wastewater streams are diluted fluorine-free salt solutions.61
It has also reported the development of a facile recycling
process via ultrasonication for catalyst-coated membranes
(CCMs) used in PEMWEs.63 The method provides high
yield recovery of not only the noble-metal catalyst materials,
but also of the fluoropolymer membrane itself, without the
release of hazardous gases.
As promising as these processes might sound, they still
require highly sophisticated instrumentation and safety
controls, making the recycling process difficult to scale up.
The key factors to be considered the most in the pursuit of an
optimized cost of ownership are tightly bound to the supply
chain improvements required to keep pace with the higher
purchase volumes. New CCM fabrication methods could help
reduce the catalyst loading, while improving the stack
efficiency and durability. Figure 19 shows a general trend
expectation for PEM electrolyzer cost. The projection was
reported by Saba et al.64 in a comparison of cost studies from
the past 30 years. In any case, such cost projections should
only be considered as relative numbers and are very dependent
on each stack and system design.
In Figure 19, the graph reports the comparison of expert
estimates on capital costs and projections rates for PEMWEs,
based on several manufacturers projection, different stack and
system designs. The breakout of the cost projection obtained
by an experts’ elicitation study conducted by Schmidt et al.8 is
reported in Figure 20.
According to Schmidt’s projections for an annual deploy-
ment on the gigawatt scale, the main drivers for the cost
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Figure 19. Expected capital cost projection for PEMWE production.
[Reproduced with permission from ref 64. Copyright 2018,
Pergamon.]
Figure 20. Relative impact of technology improvements in different
area (cell, stack, system, manufacturing, and supply chain) on capital
cost, lifetime and efficiency of PEM water electrolyzers, according to
academic and industry experts estimates. Reproduced from reference
8.
reduction are cell stack cost and manufacturing. To reduce the
latter cost, the key parameters are component standardization
and manufacturing automation, as well as new electrode
coating methods and increased production rates.
6. DEVELOPMENT OF NON-PGM CATALYSTS
The low abundance and high costs associated with PGM-based
electrocatalysts have hampered the widespread use and market
deployment of advanced electrochemical technologies such as
PEM fuel cells and electrolyzers. Within PEM fuel cells, the
R&D community have, in the last decades, intensively worked
to reduce the needed amount of platinum catalysts or hopefully
eliminate its need by using promising non-PGM based
catalysts. Significant loading reductions of platinum have
been achieved within commercially existing PEM fuel cell
vehicles; however, to date, these devices still use platinum-
based catalysts on both sides of the cell. PEM electrolyzers
suffer from a much greater challenge as its anode is dependent
on scarce iridium, an element which is 10 times less abundant
than platinum and suffers from unpredictable market-cost
fluctuations. Nevertheless, fuel cells are targeted at a much
higher number of produced units as it aims transportation and
possess much lower current densities than PEM electrolyzers.
Nevertheless, the discovery of a catalyst free from iridium that
would show both performance and durability profiles
comparable to that of iridium oxide electrodes would, beyond
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any doubt, greatly impact the field of PEM electrolyzers. Table 1. List of the Most Promising Non-PGM Catalyst
Perhaps not by directly and significantly impacting its CAPEX, Alternatives for Hydrogen and Oxygen Evolution Reaction
as these are still largely dependent from other materials and in PEMWEs
components used for stack construction (such as PTLs, bipolar
oxygen evolution reaction
plates, and needed protective layers); but an effective and hydrogen evolution reaction (HER) - cathode (OER) - anode
durable iridium-free anode catalyst would certainly take away Phosphides such as: Non-PGM oxides of:
negative preconceptions related to the deployment of PEM Ni5P4−N2P66 Si, Ti, Mn, Fe, Co, Cu, Mo,
electrolyzers at scale. But more importantly, PEMWEs free Co−Ni−P67 Ag, Sn, Te, Ta, W, Tl, Pb,
from iridium would certainly become completely independent Bi69,70
FeP68,69
from localized geographic mining regions of iridium, market CoP68,69
variations, and finally its scarcity. Ni2P68,69
Status. In the past decades, many research groups have
focused on different forms of supporting iridium on oxides of Sulfides such as: γ-MnO272
transition metals such as TiO2, SnO2, WO2.62 Ruthenium, CoS268,69
osmium, and other more active elements for OER have been NiS268,69
added to boost the performance of these catalysts. Unfortu- FeS268,69
nately, none of these alternatives have shown any level of MoS271
performance and durability close to that of iridium oxide, and
the transition-metal oxide supports have shown problems of Selenides such as: Multimetallic oxides such
catalyst dissolution and/or issues with electric conductivity. as:
These are some of the reasons why most iridium-supported CoSe268 NixMn1−xSb1.6−1.8Oy74
catalysts require a high concentration of iridium oxide, NiSe268
functioning as a path for the electrons to flow and avoiding Ni0.75Fe0.25Se268
the use of the less-conducting oxide used as support. In other Co3Se473
words, the non-PGM oxide simply works to reduce the amount
Tellurides such as: Polyoxometalates or metal
of iridium catalyst used in the electrode, but not as high molecular cluster anions76
CoP−CoTe275
electron conductive support, as is the case for the carbon black
catalyst support in PEM fuel cells.
Carbides such as:
Nevertheless, the lack of significant success with supported
Ti2C
forms of iridium oxide has not stopped the search for a non-
Mo2C
PGM form of catalyst for water splitting. For obvious reasons,
non-PGM catalysts based on nickel, iron, and cobalt used in Atomically dispersed catalysts (ADCs), such as
alkaline electrolyzers and fuel cells have served as inspiration to graphdiyne Ni/Fe,77 and graphene-trapped
create non-PGM catalysts for acidic cells. Indeed, some of Ni78 or Co79
these catalysts have shown similar performances to iridium
oxide at the liquid cell level using RDE setups, but have transition-metal oxides, formation of multimetallic alloys, and
suffered from stability issues, and complications during their organization into some specific shapes and morphologies.
electrode manufacturing so that these could not be tested One important aspect that must be considered is the
yet in a CCM configuration. Hence, well performing electrodes methodology used to access the performance of these non-
within a liquid electrolyte phase have never shown comparable PGM catalysts. Most publications only deal with the use of
performance when put together with PFSA ionomers in a three electrode setups with rotating disc experiments in liquid
CCM configuration. Challenges related to triple phase electrolyte. RDE is indeed a powerful tool to access the initial
boundary, catalyst utilization, surface area, interface resistance performance and durability of these catalysts, prescreening an
to the PTL, and electron conductivity are remaining challenges exhausting list of catalyst possibilities, but it cannot be
yet to be solved within non-PGM catalysts. considered the definitive answer to the search of non-PGM
Promising Non-PGM Catalyst Architectures. Table 1 for HER and OER in acidic media.65 In fact, most of these
lists some of the most promising non-PGM catalyst promising non-PGM catalyst options after RDE testing
architectures for both HER and OER in PEM water struggle to reach performance levels comparable to iridium
electrolyzers. The much lower overpotential for the hydrogen oxide when tested in a real single cell or stack configuration.
evolution reaction in acidic media and favorable kinetics have Moreover, RDE electrodes tested in liquid cells will typically
granted the possibility to create various alternatives for the give a measure of stability in the number of cyclic voltametric
cathode side. Hydrogen evolution in acidic media is indeed cycles, which is still not the best measure of stability
one of fastest reactions known in electrochemistry, with translatable to real electrolyzer stacks under industrial relevant
platinum remaining as the most active catalyst, but many conditions.
promising alternatives are being tested. Yet, these platinum
alternatives should show the same level of stability as platinum. 7. CONCLUSIONS
On the anode side, the high overvoltage for the OER, low pH Electrochemical devices such as batteries, fuel cells, and
provided by the ionomer, and oxygen generation create an electrolyzers are quickly becoming devices of crucial
optimal environment for oxidation. Under these conditions, importance in our society, completely changing the way we
non-PGM materials will face quick oxidation, low electrical harvest, transform, store, and utilize electricity. None of this
conductivity, and catalyst leaching. Most of these non-PGM would have been possible without advanced and transformative
alternatives for the OER involve the use of stable forms of materials and nanostructures called electrocatalysts. With the
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pubs.acs.org/acscatalysis
projected gigawatt up to terawatt deployment of PEM water
electrolyzers, it is of paramount importance to answer the
question of availability of PGM-based catalysts such as
platinum and iridium. Even though there is a good under-
standing we have enough PGMs for gigawatt electrolysis; how
do we ensure enough PGMs for the deployment of worldwide
terawatt-scale electrolyzers in a not-so-distant future? Never-
theless, platinum and iridium used to fabricate electrodes for
PEM electrolyzers are, to date, not entirely responsible for the
high capital costs attributed to these devices. Moreover, their
low abundance is not yet preventing the deployment of
megawatt systems worldwide. In contrast, other components
such as membranes, bipolar plates, PTLs, and balance-of-stack
are still significant contributors to the high costs. Moreover,
the final cost of produced green hydrogen is still largely
dependent on renewable electricity costs. Hence, we judge
voltage efficiency, and durability as first R&D priorities. This
combined to cost reduction strategies for other components
plus automation shall more quickly impact the short-term cost
of PEM electrolyzers. Moreover, the always-discussed point of
low iridium abundance and therefore marginal annual
production rate can be circumvented by further R&D in
electrode design to reach maximum catalyst utilization and low
electrode loading, combined with intelligent recycling strat-
egies for the electrodes and PFSA membranes.
We are still far from having PEM electrolyzers with non-
PGM catalysts. There are indeed some promising catalyst
platforms, but these still suffer from much lower performance
levels and durability profiles when put in contrast to PGM
catalysts. Part of the challenge lies in our current lack of
understanding of degradation mechanisms and limitations to
perform in situ characterization tests. Hence, there is a strong
need to focus on developing novel methods to in situ assess
catalyst performance and durability, so that degradation
mechanisms can be unveiled, and electrode kinetics uncovered.
Only then, novel synthesis strategies will allow us to create the
next generation of electrochemical catalysts that are free from
scarce PGM-based elements.
■
AUTHOR INFORMATION
Corresponding Author
Katherine E. Ayers − Nel Hydrogen, Wallingford, Connecticut
06492, United States; orcid.org/0000-0003-3246-1744;
Email: kayers@nelhydrogen.com
Authors
Ryan J. Ouimet − Nel Hydrogen, Wallingford, Connecticut
06492, United States
Jennifer R. Glenn − Nel Hydrogen, Wallingford, Connecticut
06492, United States
Diana De Porcellinis − Nel Hydrogen, Wallingford,
Connecticut 06492, United States
Andrew R. Motz − Nel Hydrogen, Wallingford, Connecticut
06492, United States
Marcelo Carmo − Nel Hydrogen, Wallingford, Connecticut
06492, United States; orcid.org/0000-0002-0186-317X
Complete contact information is available at:
https://pubs.acs.org/10.1021/acscatal.2c00570
Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
The authors would like to thank U.S. Department of Energy,
Energy Efficiency and Renewable Energy, Hydrogen and Fuel
Cell Technologies Office under the auspices of the HydroGEN
Consortia in the Energy Materials Network (Project No. DE-
EE0008092).
■
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