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com Current Opinion in

ScienceDirect Electrochemistry

Review Article

Key criteria for next-generation dimensionally stable

electrodes towards large-scale green hydrogen
production by water electrolysis
Watcharaporn Hoisang and Ken Sakaushi

Abstract produce gH2 have been developed, such as reforming

The dimensionally stable electrode (DSE) is one of the great- biomass material, photocatalytic water splitting, and
est inventions of the 20th century in electrochemical technol- electrolysis using a solar cell. Each approach has advan-
ogy, and its importance for our society is comparable to that of tages and disadvantages; for instance, the design of stable
insertion-type electrodes in Li-ion batteries. In the 21st century, photocatalysts that combine effective light absorption,
the need for large-scale and efficient green-hydrogen produc- charge separation, and an optimal electronic structure for
tion by a combination of water electrolysis and renewable en- water oxidation is challenging [4]. One of the most
ergies, which is necessary to achieve carbon neutrality while promising technologies to produce gH2 consists in
ensuring energy security, has created considerable demand combining water electrolysis (WE) and renewable en-
for next-generation DSEs. In this review, we discuss several ergies. This approach could occupy a key position in the
issues related to DSE materials. Although DSE is a well- energy cycle of a net-zero society (Figure 1). Although
developed technology from the view of the present industry, there are various sources to predict a wide variety of gH2
new scientific advances are still needed to meet the wide prices, almost all data so far suggests that a price range
range of modern technological criteria necessary to achieve a which is comparable to that of natural gas in 2020 will be
net-zero society. Here, we put an emphasis on (1) the choice of achieved by 2050 [5]. The dimensionally stable electrode
elements and (2) the choice of electrolyte for an efficient (DSE) is arguably one of the most important technolo-
search and discovery of novel sustainable electrode materials. gies in the 20th century [6e8]; it holds a core position in
the present industry, being involved in a broad spectrum
Addresses of electrochemical engineering processes. However, the
Center for Green Research on Energy and Environmental Materials,
current element of choice for the anode in WE systems is
National Institute for Materials Science, Namiki 1-1, Tsukuba 305-
0044, Japan Ir (IrOx for proton-exchange membrane type WE) or Co
(NiCo alloy for alkaline WE). Ir is one of the least
Corresponding author: Sakaushi, Ken ([email protected]) abundant elements on Earth. The Ir supply will likely
soon be a bottleneck for the large-scale production of
gH2, preventing the predicted very high demand from
Current Opinion in Electrochemistry 2022, 36:101136
being met. For instance, Japan plans to use 20 million
This review comes from a themed issue on Fundamental & Theoret- tons H2 per annum in 2050; assuming it will all be
ical Electrochemistry (2022)
gH2dproduced by WEdthe consumption of 180 million
Edited by Rama Kant and M.V. Sangaranarayanan tons per annum of water will be required, and of course, a
For complete overview about the section, refer Fundamental & large quantity of DSEs will be necessary. Therefore,
Theoretical Electrochemistry (2022) novel DSEs based on abundant elements are urgently
Available online 14 September 2022 needed [9,10]. The choice of electrolyte is also critical:
https://doi.org/10.1016/j.coelec.2022.101136 the combination of electrolyte and DSE determines the
2451-9103/© 2022 Elsevier B.V. All rights reserved. electrochemical performances, such as activity, selec-
tivity, and duration. The environmental impact must also
be considered: the present large-scale alkaline WE pro-
Keywords
Hydrogen evolution reaction, Water electrolysis, Electrocatalyst,
cess uses highly concentrated KOH, which is highly
Abundant element, Green hydorgen. corrosive and must be handled in expensive systems.
These two main issues need to be addressed to achieve
Introduction the preparation and industrial deployment of next-
Green hydrogen (gH2) is one of the key emerging fuels generation DSEs.
for achieving carbon neutrality while maintaining energy
security [1e3]. So far, hydrogen has mainly been pro- WE system consists of two half-reactions: the hydrogen
duced from natural gas by the steam reforming process or evolution reaction (HER) at the cathode, and the
obtained as a sub-product at chemical plants. Because of oxygen evolution reaction (OER) at the anode [11e14].
a limitation of fuel sources, alternative ways to effectively The OER is plagued with low kinetics; it follows a

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2 Fundamental & Theoretical Electrochemistry (2022)

Figure 1

Schematic illustration of the production of green hydrogen by combining renewable energy and water electrolysis.

complex mechanism that includes a four-electron stability of metal oxide-based electrocatalysts in elec-
transfer. The corresponding high activation energy re- trolytes over a wide range of pHs.
quires the application of a potential larger than the
equilibrium potential (1.23 V vs. a reversible hydrogen Choice of elements
electrode (RHE) at 25
C): this is one of the major Platinum-group-metal-based materials
limitations to the energy efficiency of the overall WE OER electrocatalysts have long been the subject of
reaction [11,15]. Research on the microscopic OER continuous research exploring a variety of elemental
electrode process can be traced back to the 19th cen- compositions, electronic structures, and morphologies
tury; since then, it has been the subject of a large [23e26,37]. The electrocatalytic performance of OER
number of investigations and is even applied to a wide catalysts may generally be evaluated using standard
spectrum of industrial processes [16e19]. Neverthe- electrochemical parameters in water electrolyzers. In
less, the OER is far from being fully understood. this section, we focus on approaches based on under-
Therefore, even today, efforts are still needed to unveil standing the influence of the elemental components of
and understand the relationship between the elemental the OER electrocatalysts on their activity and long-term
composition of an electrocatalyst and its electro- durability in the hostile electrochemical system.
chemical properties so as to optimize its activity and Figure 2(a) shows how the activity and stability of noble
stability [20,21]. High-performance DSEs can be metal-based OER electrocatalysts depend on the type of
designed using two basic strategies: the first strategy is element in the electrocatalyst and its material feature.
to tune the intrinsic activity of the investigated elec- More noble materials (such as Au) are less active (higher
trocatalysts by exploiting the electronic structure of the overpotential) but more stable (lower concentration of
different elements, which is correlated with the dissolved metal cations) than other oxides. Moreover,
adsorption energy of oxygenated intermediates to the the amorphous phases show higher activity compared to
electrode surface [22], and the second one is to in- crystalline phases. The OER activity shows a pro-
crease the number of active sites. Although the selec- nounced positive correlation with the adsorption energy
tivity of the OER is also of great importance, in this between the metal (active site) and the oxygenated
review, we focus on the strategy to improve the elec- species, which is believed to control the OER kinetics,
trochemical properties, activity and stability of OER but is often negatively correlated with the stability of
electrocatalysts by tuning their elemental composition. the electrocatalyst; a trade-off between stability and
The influence of the nature of the electrolyte in acidic, activity is then necessary [38,39]. In addition, the sur-
neutral, and alkaline environments on the stability and face defects are also thought to play a critical role in
activity of OER electrocatalysts is then discussed. controlling the stability and activity of the OER [38].
Finally, an outline of the challenges and perspectives for Indeed, volcano plots can be constructed from the OER
the future development of OER electrocatalysts is activity and either their enthalpy of oxide transition
given. Although various reviews focusing on OER (Figure 2(b)) [40,41] or the adsorption energy between
electrocatalysts have been published [23e36], this the active intermediates and the corresponding surface
review focuses on the correlation of activity and (Figure 2(c)) [22]. When the adsorption energy

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 Next-generation dimensionally stable electrodes Hoisang and Sakaushi 3

Figure 2

Representative relationships between OER activity and other properties in various electrode materials. (a) Left: relationships between the OER
activity and stability of different metallic oxide materials. EC: amorphous electrochemical oxide. TC: crystalline thermal chemical oxide. Middle: structure
of the amorphous (EC) oxide and crystalline (TC) oxide. Right: I–V curves of single crystals (Ru (0001), and Ir (111)) and polycrystalline electrodes (IrO2
and RuO2). Reprinted with permission from Danilovic et al. [38] Copyright (2014) American Chemical Society. Volcano plots: activity trends for the OER as
a function of (b) the enthalpy of transition from a lower to a higher oxidation state. Measurements in alkaline medium are shown as open symbols and
measurements in acidic medium as filled symbols. Reproduced with permission from Trasatti et al.[41] Copyright (1984) Elsevier; and (c) the free energies
of DGO* − DGOH* for rutile and anatase oxides. The activity is expressed as the value of the overpotential needed to achieve a certain value of current
density. Reproduced with permission from Man et al. [22] Copyright (2011) WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

between the metal-oxide active site and the oxide in- reactive oxygen species with high electrophilicity
termediate and the energy of oxide transition are perform a critical role in the formation of OeO bonds
optimal, oxygen evolution occurs at a low overpotential. during the OER [49]. In a study on IrO2- and RuO2-
based nanoparticles, both exhibited higher OER activ-
Among the OER electrocatalysts from the volcano plots ities in an acidic electrolyte (0.1 M HClO4) than in an
in Figure 2(b,c), platinum-group-metal-based (PGM- alkaline electrolyte (0.1 M KOH) [48]. Because RuO2
based) oxide materials have attracted tremendous has more optimal adsorption energies between the
attention and have been widely explored, with the aim active surface sites and OER intermediates [39], the
of boosting catalytic performance [6,41e45]. In partic- overpotential of RuO2 is slightly lower than that of IrO2.
ular, iridium oxide (IrO2) and ruthenium oxide (RuO2) Conversely, the IrO2 electrocatalyst exhibits higher
are among the most active material reported to date; stability under anodic potentials than RuO2, but these
they are considered the benchmark OER electro- materials are still unstable: for both IrO2 and RuO2,
catalysts [46,47]. They can adopt a rutile structure or a metallic cations at high oxidation states readily dissolve
hydrated amorphous structure [48], in which surface into the electrolyte [50].

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4 Fundamental & Theoretical Electrochemistry (2022)

Doping metal oxides and oxyhydroxides with hetero- leaching. Even though the PGM-based electrocatalysts
atoms significantly improves the electrocatalytic prop- exhibit high OER performances, their large-scale
erties of the host material via a change in active site and application remains limited by the high cost and scar-
an increase in surface defect density. Based on this city of PGMs.
observation, many groups have investigated multicom-
ponent materials in the search for electrocatalysts with Platinum-group-metal-free transition metal-based
the best compromise between catalytic activity and materials
stability. In the early days of OER electrocatalysts PGM-free OER electrocatalysts, such as 3d transition
development, because of the low stability of PGM- metal oxides and hydroxides, have recently emerged and
based oxides in acidic environments, binary are already attracting widespread attention on account
conductingeinsulating material systems were devel- of their abundance, great stability, and tunable struc-
oped [51,52]. The hybridization of conducting materials ture. These materials may exhibit high electronic con-
(IrO2, RuO2, or Pt) with inert oxides (Ta2O5 or ZrO2) ductivity, activity, and stability depending on the type
was found to be able to provide both stability and high and oxidation state of the metal(s) they contain. In
electrocatalytic activity thanks to the ability of the inert particular, the OER activity and stability of 3d-transition
oxide to preserve the active surface of the conducting metal-containing electrocatalysts are strongly impacted
metal oxides. Still with the aim of finding the best by changes in their electronic structure, in consistency
compromise between activity and stability, several with the dependence of the adsorption energy on the
binary metal oxides were prepared by incorporating a catalytic surface described by d-band center theory
small amount of a transition metal, such as Mn, Cu, or Y, [61,62]. In this section, we summarize the OER cata-
into an IrO2 host material [53e55]; their OER perfor- lytic performances of the recently developed PGM-free
mance was very effectively increased over that of the oxides/oxyhydroxides-based electrocatalysts and
original material, an improvement attributed to their compare them with PGM-based electrocatalysts. It
higher electrochemically active surface and the higher should be noted that here, we focus on electrocatalytic
intrinsic activity of the defect sites of the doped IrO2 properties at room temperature. We are also concerned
electrocatalysts. For example, binary IreCu metal with the correlation between the stability of the mate-
oxides (IrxCu1-xOy) showed excellent stability and rials, evaluated from the variation in overpotential values
electrocatalytic OER activity [53]. The number of at given current densities, and the pH of the electro-
oxygen vacancies and the presence of Ir3þ species in- chemical system.
creases with the incorporation of Cu, as Cu is more easily
oxidized than Ir and creates lattice distortions leading to Figure 3(a) shows the electrocatalytic stability at various
a greater number of defect densities. An IrxCu1-xOy current densities against the pH of the electrolyte, and
catalyst showed a low overpotential toward the OER Figure 3(b) shows the trend in specific charge density
(<358 mV) at 10 mA/cm2; this overpotential was shown (ranging from 1 kC/cm2 to >1 MC/cm2), which can be
to be independent of pH after being evaluated in acidic calculated by using the stability of the electrocatalyst
(0.5 M H2SO4), neutral (1.0 M phosphate buffer solu- over time at a specific current density. The perfor-
tion; pH 7.2), and alkaline (1 M KOH) conditions. The mances of Ir-based DSEs (IrO2, IrO2/Pt, and IrO2/
overpotential was only increased by about 10 mV even Ta2O3), used as benchmark OER electrocatalysts, are
after 6 h at 10 mA/cm2, in contrast with IrO2/Ir nano- presented alongside those of the PGM-free materials.
fibers and commercial Ir/C, which are examined to be For example, IrO2 and IrO2/Ta2O3 respectively shows
unstable at all pH values. Additionally, OER electro- good stability during 120 and 4000 h at 1 A/cm2 (1M
catalysts consisting of complex multimetallic Ir- or Ru- H2SO4 at 50
C), respectively.
based metal oxides (perovskites) display high activity
and stability in acidic conditions [56e58]. Partial doping Typically, 3d transition metal oxides (Ni, Co, Mn, Fe,
with mono- or divalent cations, such as Cuþ, Kþ, and etc.) are promising sustainable electrocatalysts for the
Zn2þ, leads to changes in the lattice geometry, affecting OER in alkaline conditions, as seen in Figure 3(a)
the structural symmetry of the perovskite oxides, and to [25,63e65]. During the electrochemical process, the
the formation of higher oxidation states of the active structure of 3d-transition metal-based oxide materials is
metals (Ir or Ru). These changes promote an increase in generally transformed into a high-surface-area structure
intrinsic activity and a decrease in the dissolution of of hydroxide/oxyhydroxide layers [66,67]. Hence, the
oxidized metal cations on account of the lower partici- activity of the reaction is not limited to only active
pation of lattice oxygen redox reactions in the OER surface sites but may also involve the intercalation of
[57e59]. For instance, SrIr1-xZnxO3 perovskite struc- water molecules and anions in the catalyst, because of
tures exhibited good OER stability over 15e18 h at the weak interaction between layers of hydroxide/
10 mA/cm2 [56]. During the OER, the catalyst under- oxyhydroxides, which may enhance the OER electro-
went surface reconstruction [33,34,60]: the surface area catalytic performances. Trotochaud et al. studied the
increased and amorphization occurred, that is, resistive OER electrocatalytic properties of thin films of metal
amorphous material was generated because of dopant oxides and found that the in situ transformation from

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 Next-generation dimensionally stable electrodes Hoisang and Sakaushi 5

Figure 3

Electrocatalyst stability–activity trends for reported OER catalysts in recent years. (a) Electrocatalyst stability against electrolyte pH various current
densities, and (b) electrocatalyst stability against current density at various electrolyte pH values. The data ( ) obtained from the studies by Kim et al.,
Edgington et al., Miao et al., Vij et al., Li et al., Pan et al., Chen et al., Chen et al., Che et al., Chen et al., Li et al., Li et al., Zhang et al., Zhou et al., Wei
et al., Laha et al. [53,56,58,63,68,70,72,73,78,79,81,82,84–86,89] is compared with benchmark Ir-based DSEs (⚈) obtained from Masuko et al. [90].
These benchmark DSEs consist of Ti substrates with a fixed electrocatalyst loading of ca. 10 g/m 2; they were operated in 1 M H2SO4 at 50
C. The data
for the other materials were mostly obtained at around 25
C. We also note here that one of present commercialized largescale alkaline water elec-
trolyzers shows an operation current density of 600 mA/cm2 with a cell voltage of 1.78 V at < 90
C in 30% KOH solution.

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6 Fundamental & Theoretical Electrochemistry (2022)

NiO to Ni(OH)2/NiOOH could occur during the elec- of Cu-doped Co3O4 was studied in KOH electrolyte
trochemical reaction (under alkaline conditions) [66]. solutions (pH 11 to 14) [71]. At increasing pH, the
The transformation was demonstrated by the evolution current density increases, up to ca. 310 mA/cm2 (at 1 V
of the voltammogram of NiO after a prolonged time: it vs. Ag/AgCl) at pH 14, which indicates that high OHe
indicates an increase of Ni2þ oxidation to Ni3þ, which concentrations promote the electrocatalytic oxidation of
leads to an increase in OER activity. As depicted in water on the catalyst. Stability is an essential aspect of
Figure 3(a), such a double-layer NiFe(OH)2 electro- the evaluation of an electrocatalyst, because its practical
catalyst provided better stability at high current density application involves long-term utilization at high current
(1 A/cm2) and in alkaline conditions than other materials density. Ternary CoeFeeV metal oxide Co3Fe4V3Ox, a
based on metal oxides [68]. Besides, its high activity and multicomponent Co-based electrocatalyst, showed
stability are mainly attributed to dual-active sites on the excellent stability, maintaining a low overpotential
surface of the two metals (Ni and Fe). Recently, (249 mV) at 50 mA/cm2 for at least 72 h in an alkaline
Schoen’s group reported synergistic effects on the effi- electrolyte [72]. From density functional theory (DFT)
ciency of OER in an amorphous NiFeOx material [69]. A calculations, the author determined that the introduc-
combination of spectroscopic and electrochemical ana- tion of iron (Fe) and vanadium (V) can strongly enhance
lyses of NiFeOx suggested that the dependence of the the electron density of the Co active sites and change
potential determining step on the annealing tempera- the adsorption energy of OER intermediates. Based on
ture correlates with structural transitions at the Ni site, spectroscopic data, the inverse spinel phase of this
while the kinetics of the reaction correlate with struc- ternary Co-based oxide is defective and distorted by the
tural transitions at the Fe site. Accordingly, the OER incorporation of heteroatomic Fe and V, which fill the
would take place at the dual catalytically active sites tetrahedral sites. After an OER stability test, some of
consisting of Ni and a neighboring Fe surface. These the V species had leached out while the Co and Fe ratio
sites are thought to be responsible for the remarkable remained, causing only minor surface reconstruction.
decrease in overpotential value (<200 mV) at 10 mA/ However, the metal oxide catalyst retained its amor-
cm2 observed over the binary NiFeOx material under phous structure without element/crystal phase segre-
alkaline conditions, which indicates a higher OER gation, suggesting a high stability. In summary, the great
activity than over the corresponding monometallic OER performances of ternary CoeFeeV metal oxides
electrocatalysts. originate from the intrinsic activity of the materials. Co-
based ternary CoeFeeW metal oxyhydroxides exhibit
Binary and multinary 3d-transition metal-based mate- excellent OER catalytic activity in harsh electrolyte
rials have been investigated as alternative OER elec- conditions [73]. In alkaline electrolyte (1 M KOH), a
trocatalysts owing to their great activity and long-term CoeFeeW electrocatalyst coated on Ni foam delivered a
durability; recent development have focused on high current density of 500 mA/cm2 at a small over-
expanding the range of electrochemical reaction condi- potential of 280 mV and showed excellent stability over
tions they can withstand. Here, we summarized the 48 h; at an overpotential of 234 mV, it delivered 100 mA/
application of some multicomponent materials based on cm2 during 120 h. The OER performance of this elec-
metals such as cobalt (Co), nickel (Ni), manganese trocatalyst was further investigated in seawater, a near-
(Mn), as well as high entropy materials for the OER neutral electrolyte (pH = 8.4, conductivity = 32 mS/
process. Various Co-based binary metal oxides have been cm); it required an overpotential of 422 mV to reach
explored as OER electrocatalyst candidates [65]. For 100 mA/cm2. Furthermore, the CoeFeeW electro-
example, Pan et al. studied the effect of the cerium (Ce) catalyst was also shown to be remarkably stable in a
content on the OER performance of binary electro- practical alkaline-water electrolysis system (at 500 mA/
catalyst Co1-yCeyOx [70]. A remarkable improvement in cm2 in 10 M KOH electrolyte at 80
C) with remarkable
OER activity was observed when the Ce amount was stability. The high OER performance of the CoeFeeW
less than 60% (where y  0.6). X-ray photoelectron electrocatalyst derives from an increase in intrinsic ac-
spectroscopy (XPS) and cyclic voltammetry (CV) tivity and surface-active area, obtained by increasing the
revealed that increasing the Ce content led to an in- number of octahedral coordinated trivalent cobalt cat-
crease in the number of Co3þ sites and an increase in ions (Co3þ) working as electrocatalytic active sites, and
metalehydroxyl (MOH) bond strength. The addition from their amorphous crystalline structure. DFT calcu-
of Ce modifies the electronic structure of the active lations reveal an upward shift in the d-band center of Co
species of Co via a charge transfer to neighboring oxygen 3d and the p-band of O 2p electron, as well as a decrease
species. A Co0.6Ce0.4Ox catalyst supported on a fluorine- in the energy gap between these two-band centers, after
doped tin oxide (FTO) coated glass substrate showed an the addition of Fe and W into ternary host materials.
overpotential of 320 mV at 10 mA/cm2 in 1 M KOH This suggests that the stabilized adsorption energies of
solution and an OER durability of at least 100 h at 5 mA/ OER intermediates at Co active sites and low electron
cm2. Hence, the binary Ce-added CoOx exhibited long- transfer resistance are the main reasons for the
term durability in addition to increased OER activity. enhancement of the OER electrocatalytic performances.
Moreover, the effect of alkalinity on the catalytic activity Hence, after the incorporation of heteroatoms in the
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 Next-generation dimensionally stable electrodes Hoisang and Sakaushi 7

Co-based electrocatalyst, the electronic structure of Co using in situ UV/Vis electrochemical spectroscopic mea-
in the oxide/oxyhydroxide catalyst has adsorption en- surements [81]. Absorption signals assigned to the
ergies that are nearly optimal for the reaction in- active Mn3þ sites were clearly detected at the near
termediates in the OER, resulting in its superior activity onset potential of the OER, while a new absorption
and stability [72e75]. feature attributed to MnOe 4 appeared at a high potential
value (>1.8 V vs. RHE). These results indicate that
Ni-based materials are among the most active OER under strongly acidic conditions and in the high poten-
electrocatalysts, with catalytic activities comparable to tial region, the dissolution of MnO2 does occur resulting
those of RuO2 and IrO2 [76]. The synergistic effect be- in a change in intrinsic activity and the number of sur-
tween Ni and neighboring heteroatoms dramatically face sites [80,81]. However, Mn-based metal oxides still
improves the adsorption ability of the active-site surface exhibit high stability as OER electrocatalysts at poten-
of the catalyst, thus enhancing its OER electrocatalytic tials lower than the onset potential of MnOe 4 formation.
properties [63]. A study reported the incorporation of
other transition metals into Ni(OH)2; electrocatalysts Although single, binary, and ternary metal-based mate-
deposited on Ni microdiscs showed OER activity in- rials have demonstrated good catalytic performances for
creases in the order Cu2þ < Mn2þ < Cr2þ < Co2þ < Fe2þ OER, their poor stability hampers their application in
[68]. The Ni/Fe(OH)2 electrocatalyst delivered a practical industrial systems. Moreover, the flexibility in
notable high current density of 500 mA/cm2 at the lowest electrocatalyst design is limited to a restricted number
overpotential, 265 mV in a 1 M NaOH aqueous solution. of elemental compositions and metal types. To address
Furthermore, OER stability was evaluated under a cur- these issues, great efforts have been devoted to the
rent density of 1 A/cm2 for the Ni/Fe(OH)2 electrode, design and synthesis of multinary metal-based com-
which was delivered at a potential of 2.12 V (vs. RHE); plexes and high-entropy materials (HEMs) as electro-
the material shows long-term durabilitydat least catalysts. In particular, the PGM-free HEMs for OER
240 hdunder alkaline electrolytic conditions (4 M catalysis have recently attracted research interest owing
NaOH at 60
C). This high stability may be due to the to their excellent material properties, such as high
oxidation state of nickel and iron (Ni2þ and Fe3þ), which corrosion resistance, surface chemistry complexity, and
are much closer to the oxidation states in the OER region tunability [83]. For example, CoNiFeCu electrocatalyst
[77]. For nanohybrid electrocatalyst (FeeNi)Cox-OH/ exhibited high OER activity, and the stability of this
Ni3S2, the combination of Ni2S3 S-vacancies with ternary material was comparable to that of RuO2, withstanding
(FeeNi)CoxeOH yielded great catalytic performances 120 h at 500 mA/cm2 in a strongly basic electrolyte (7 M
in the OER, with an overpotential of 280 mV at 100 mA/ KOH at 50
C) [84]. Interestingly, the authors reported
cm2 and a durability of at least 100 h at 200 mA/cm2 in an initial decrease in overpotential, which then
alkaline electrolyte [78]. The electrolytic OER activity remained constant after a few hours of electrocatalysis;
of Ni-based materials is not limited to alkaline media but this behavior suggests the occurrence of surface activa-
is also observed in pH-neutral solutions. An OER elec- tion originating from the corrosion of amorphous carbon
trocatalyst made of amorphous NiCoeB(OH)4 directly and from Cu leaching, which improves the number of
coated on Ni foam showed an overpotential of 430 mV at active sites and the intrinsic OER activity.
10 mA/cm2 in 0.1 M KB(OH)4 electrolyte (pH = 9.2),
and its catalytic activity was maintained for 20 h [79]. Due to the diverse valence states from multi-elemental
Although Co-, Ni-, and Fe-based oxides and hydroxides components and a suitable nanostructure, most of the
exhibit high OER performance in alkaline conditions, reported HEM-based OER electrocatalysts exhibit a
they are not stable in acidic electrolytes, in which they relatively low overpotential and remarkable long-term
readily dissolve [24,26]. durability at high current density in alkaline media
(here we show only the results in 1 M KOH solution);
Mn-based oxide compounds, such as g-MnO2, are OER for example, an Fe50Mn30Co10Cr10 honeycomb alloy
electrocatalysts that show high corrosion resistance in showed an overpotential of 247 mV at 10 mA/cm2 and
acidic environments; they were reported to be kineti- stability up to 60 h at 100 mA/cm2 [85], and an FeCo-
cally stable in H2SO4 solution [80]. For instance, a NiPB/(FeCoNi)3O4-x ribbon composite showed an
MnO2 electrocatalyst coated on FTO exhibited overpotential of 229 mV (to reach 10 mA/cm2) and is
extraordinary long-term stability: more than 8000 h at a stable for at least 25 h at 350 mA/cm2 [86]. Such
current density of 10 mA/cm2 at pH 2, and about 120 h nanostructures enlarge specific surface areas and thus
at a current density of 100 mA/cm2 [81]. The durability enrich active site density that is believed to improve the
of heterogeneous OER electrocatalyst Co2MnO4 was OER activity. In addition, by incorporating heteroatoms
also studied at high current densities in acidic media; it in the materials, more high-valence statesdacting as
showed a lifetime of more than 2 months (>1500 h) at active sitesdcan be generated during the redox reaction
200 mA/cm2 in an electrolyte at pH 1 [82]. Li et al. of the OER electrode process, which influences the
investigated the activity and stability of the g-MnO2 electrocatalytic activity of the HEMs. High-entropy
phase during the OER process under acidic conditions metal oxides (HEOs) nanoparticles, such as
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8 Fundamental & Theoretical Electrochemistry (2022)

FeCoNiMnBOx [87] and (FeCoNiCrMn)3O4 [88], have their free energy of adsorption on the Pt (111) catalytic
also been demonstrated to be active OER electro- surface, as shown in Figure 4 (a, b). ClO4e binds to the
catalysts with outstanding stability: almost 100 h at surface sites with the weakest adsorption energy,
10 mA/cm2 in 1 M KOH. By combining the benefits of followed by NO3e and SO42, according to the physical
multiple elements (structure stability, surface recon- properties of the anions and their intrinsic behavior
struction, and defect structure) these PGM-free elec- within the active sites [95], which indicates that with
trocatalysts, being multi-component metal oxides, ClO4e, less anion adsorption occurs relative to oxide
successfully achieve a high charge density (>10 kC/ coverage as compared with other anions. Additionally,
cm2) over the whole pH range and exhibit low over- competitive adsorption effects dominate in the OER
potential and high long-term stability, comparable to potential region, although non-adsorbed-anion in-
that of the benchmarked IrO2-based DSE, as illustrated teractions, such as electrostatic interactions, are likely to
in Figure 3(a, b). Therefore, we believe that the selec- occur as well. The OER activities in the electrolyte
tion of elemental composition is one of the most followed the order of HClO4 > HNO3 w H2SO4, while
important features in the design of prospective elec- overpotential values followed the reverse order, in line
trocatalysts for water electrolysis application; it could with the binding energies of the corresponding
prove essential in addressing some of the current issues anions [95].
of traditional materials.
The electrolyte composition also has a significant effect
Choice of electrolytes on the electrocatalyst stability. For instance, the OER
It has long been known that the understanding of the performance of cobalt-based oxides (CoPbOx and
reaction mechanisms is essential for the design of CoFePbOx) was evaluated in two buffer electrolytes
effective OER electrocatalysts [17,18,91,92]. In- containing 1 M KNO3 and either phosphoric (H3PO4*/
vestigations on the interactions between reaction in- KH2PO4, pKa* = 2.15) or sulfuric acid (H2SO4*,
termediates and the electrode surface and their KHSO4/K2SO4, pKa* = 2.00) [96]. In both cases, an
influence on the catalytic activity, selectivity, and sta- increase in electrolyte concentration resulted in only a
bility have been recently reported [37,93]. Besides slight decrease in stability. The bulk solution pH,
these influences, the electrocatalytic activity also de- however, had a much pronounced effect. In acidic
pends on the composition and pH of the electrolyte. media, the electrocatalysts operating in the phosphate
Theoretically, the OER is one of two half-reactions in buffer displayed much better stability than those in
water splitting; it is a four-electron process that pro- sulfate buffer. Interestingly, as the pH of the phosphate
ceeds differently under acidic (Equation a) and alkaline electrolyte was lowered from 4.03 to 1.03, the stability of
(Equation b) conditions. the electrocatalyst (operating at a current density of a
1 mA/cm2) initially experienced a small decrease be-
Acidic conditions: 2H2O / O2 þ 4Hþ þ 4ee (a) tween pH 4.03 and pH 2.15, followed by a precipitous
decrease between pH 2.15 and pH 1.03; this instability
Alkaline conditions: 4OHe / O2 þ 2H2O þ 4ee (b) at low pH was attributed to a drop in concentration of
monobasic phosphate (pKa of the conjugateddphos-
phoricdacid = 2.14), which can play an essential role in
The reaction pathways can be altered by the choice of stabilizing the active sites of the catalyst. Indeed, unlike
electrocatalyst and of electrolyte. In this section, we the sulfate electrolyte, the phosphate electrolyte binds
focused on the influence of various electrolytes on the oxide surfaces with high affinity via hydrogen bonding; it
OER performances; the interactions between electro- provides protection to the edge sites of the metallated
catalyst (mainly on PGM-free materials) and electro- clusters, preventing the dissolution of the active sites
lytes will be briefly discussed. and promoting self-healing. Hence, by performing the
OER in different electrolytes and at different pHs and
Acidic electrolytes buffer concentrations, the authors demonstrated that
The OER pathways have been reported to broadly the long-term durability of the CoFePbOx electro-
follow the adsorbate evolution mechanism (AEM) and catalyst in acidic conditions was significantly influenced
the lattice oxygen evolution reaction (LOER) mecha- by the nature of the electrolyte.
nism [18,26,59,94]. In the AEM mechanism, the
adsorption of oxygen intermediate species with Alkaline electrolytes
different binding energy on the active sites is one of the OER catalysis has been mostly conducted in alkaline
key processes that determine the catalytic performance media because of the stability of non-noble metal-based
and behavior of the OER electrocatalyst. Recently, it was catalysts under these conditions, as clearly shown in
found that different electrolyte anion species (H2O/ Figure 3(a). The OER performance in alkaline media is
OHe/O2e, NO3e, HSO4e/SO42, and ClO4e) under also relatively sensitive to the electrolyte composition
acidic conditions (pH 1) displayed a different trend in [97e100]. To shed light on this phenomenon, the impact

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 Next-generation dimensionally stable electrodes Hoisang and Sakaushi 9

Figure 4

(a) Illustration of the adsorption configuration of some electrolyte anions on the Pt (111) surface (elemental labels; O: red, H: white, Cl: green, N: blue, and
S: olive green). (b) The adsorption free energies (DGadsorption) of anion species (H2O/OH – /O2−, ClO4 −, NO3 −, and HSO4 −/SO4 2−) on the Pt (111) surface
as a function of applied potential (V vs. RHE). Reproduced with permission from Kamat et al. [95] Copyright (2022) Springer Nature. (c) Schematic
illustration of ionic interactions between the components of a KOH–NaNO3 electrolyte and (d) LSV curves at 2 mV/s in various KOH–NaNO3 electrolytes.
Reprinted with permission from Li et al [103] Copyright (2019) American Chemical Society.

of the alkaline cation, typically Liþ, Naþ, or Kþ, on the interactions between the additive and the components
OER activity of perovskite Ba0.5Sr0.5Co0.8Fe0.2O3ed of the electrolyte. Because Naþ has a stronger covalent
[101], rutile IrO2 [101], and RuO2 was investigated interaction with OHe than Kþ, a lower number of active
[102]. In an alkaline solution, the OER activity of the OHe species is bound to the metal site surface. This
catalyst increases with increasing cation size, that is, in leads to a decrease in OER activity as the NaNO3:KOH
the order Liþ < Naþ < Kþ. Because of the solvation ratio is increased while maintaining the salt concentra-
environment of cations, the activation enthalpy is larger tion constant, as shown in Figure 4(d). In alkaline con-
in the electrolyte containing Liþ than in those containing ditions, the alkaline cation species and their
Naþ or Kþ, as determined by temperature-dependent concentration significantly impact OER performance,
kinetic measurements [102]. Because its small ionic because of differences in the intrinsic properties of the
radius, Liþ can strongly bind with water molecules in the electrolyte, such as ionic conductivity and number of
hydration shell and further interact with cationic active active sites.
sites, in contrast with large Kþ ions. Hence, a greater
number of active sites and OHe species from isolated Near-neutral electrolytes
water molecules are observed in the KOH electrolyte Besides acidic and alkaline electrolytes, near-neutral
environment, resulting in an increase in OER activity. electrolytes and their influence on various OER elec-
Moreover, the effect of electrolyte composition was trocatalysts (such as metal-based oxides [53,104,105],
studied in the electrical double layer (EDL) structure of hydroxides [106], borates [79,107], and nitrites [108])
the IrOx, that is, the catalysteelectrolyte interface, have been widely studied on account of the large
during the OER [103]. Introducing NaNO3 as an addi- working potential window of neutral electrolytes, their
tive into the KOH electrolyte increases the ionic con- low toxicity, and the low corrosion rate of OER elec-
ductivity, adsorption of OHe, and transportation of O2 in trocatalysts in neutral media. However, such conditions
the EDL structure. Figure 4(c) illustrates the ionic lead to low OER activities, because of problems such as

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10 Fundamental & Theoretical Electrochemistry (2022)

pH-dependent electrocatalytic activity, limited reactant electrolyte environment is an important strategy that
diffusion, and low electrolyte conductivity, which are needs to be the focus of further research efforts.
especially critical at current densities of >100 mA/cm2.
In order to address these issues, the introduction of Conclusions and outlook
buffer species into near-neutral pH electrolytes has In this review, we summarized the design of state-of-
been reported, using IrOx as an electrocatalyst model the-art OER electrocatalysts and electrolytes for the
[105]. In a 1 mol/kg Na-based buffer electrolyte enhancement of catalytic activity and stability, a ne-
containing phosphate (pH 7.0), borate (pH 9.2), or cessity for the development of future industrial appli-
carbonate (pH 10.3), the overpotential at 10 mA/cm2 cations. The main conclusions are the following:
largely decreased with increasing temperature
(25e70
C) than in a 0.1 mol/kg NaOH electrolyte (pH (i) PGM-based electrocatalysts can show both high
12.9). This study suggests that OH is the reactant in activities and stabilities therefore applied to large-
the buffered conditions and buffering species work to scale WE systems. Electrocatalytic activity de-
maintain the local pH by supplying OH during the pends on the adsorption energy of the active in-
OER electrode process. More details on the effect of termediates with the electrode surface; their
buffering were provided by rigorous microkinetic anal- relationship follows the Sabatier principle and can
ysis: the authors found that the buffer species regulates be represented as a volcano plot. The incorporation
the concentration of OH at electrode surface constant; of different neighboring cations shows an increase
OH is likely the kinetically relevant reactant for the in activity. We note, however, that recent studies
OER in the near-neutral buffer condition [105]. Beyond question the simple application of the Sabatier
the direct influence on catalytic performances, some principle to electrocatalysis at solideliquid in-
buffer electrolytes (such as phosphates or borate) can terfaces [116,117].
promote the self-assembly of metal cation species (such (ii) PGM-free electrocatalysts (mainly involving 3d-
as Co2þ or Ni2þ) into active metal-based OER electro- transition metals) have reached high OER stability
catalysts under mild reaction conditions [109e112]. and activity; their activity is comparable to that of
Because the OER includes a proton-coupled electron benchmark IrOx-based DSA. As same as in the case
transfer, pH has a significant impact on the formation of of PGM-based materials, their intrinsic OER ac-
intermediate components (hydrogen phosphate ion as tivity tends to depend on the adsorption energy
the proton acceptor) and controls the rate-determining between electrode surface and the active species;
step of the OER and hence the degree of catalytic ac- this correlation provides an opportunity to tune
tivity. By investigating the electrode kinetics across a their OER properties by exploiting the complexity
near-neutral pH range, these studies revealed the of multicomponent electrocatalysts however in
importance of buffer species to OER performance. same time is a limitation to design new materials.
The synergetic effect of multiple elements may
The effect of seawater composition on OER efficiency provide structural stability and induce surface
has also been studied [113,114]. The chlorine evolution reconstruction, and these effects modify the ac-
reaction was predominant in the seawater (NaCl) elec- tivity of the PGM-free electrocatalysts. Therefore
trolyte at a large current density, which decreased the PGM-free high-entropy and multi-element mate-
selectivity for the OER. In addition, cationic and anionic rials are of particular interest as DSEs for the OER.
contaminants in seawater interfere with the OER ac- (iii) The choice of cation/anion in and pH of the
tivity owing to their differences in ionic conductivity or electrolyte have a considerable influence on the
the side reactions they provoke, as previously explained OER performances. Differences in electrolyte
[115]. However, notwithstanding the great develop- environments are suggested to have an effect on
ment of electrocatalyst materials and the recent studies the interactions between the electrode surface
on electrochemical conditions, much remains to be and ionic species in the electrolyte; this induces
done: more refined methods for the determination and changes in the OER activity and stability of the
characterization of the active site(s) on the surface of electrocatalysts.
multinary materials must be developed, the reaction and
dissolution mechanisms must be better understood, and
materials that exhibit high activity and stability across In addition to the above, although we did not discuss
the whole pH range must be designed. In particular, the them here due to the limited space, the meso-/macro-
long-term stability of the electrocatalysts under high scopic design of the electrode structure and the preven-
potential and current densities, necessary for industrial tion of degradation due to voltage fluctuation will also be
applications, remains a challenge. To overcome these important factors in achieving the industrial scale pro-
issues and develop OER applications, the use of new duction of gH2. Moreover, from the point of view of the
electrocatalyst materials combining the advantages of industry, besides having high activity and stability, the
elemental types associated in a suitably designed OER electrocatalysts should be made of Earth-abundant

Current Opinion in Electrochemistry 2022, 36:101136 www.sciencedirect.com

 Next-generation dimensionally stable electrodes Hoisang and Sakaushi 11

elements at a low production cost, so as to be economical This report discussed on material chemistry of porous solid-state ma-
terials based on carbon and nitrogen for preparing a next-generation of
and eco-friendly. Therefore, further investigations are sustainable electrode materials.
needed for the development of DSE materials.
11. Zeng K, Zhang D: Recent progress in alkaline water electrol-
ysis for hydrogen production and applications. Prog Energy
Combust Sci 2010, 36:307–326.
Declaration of competing interest
The authors declare the following financial interests/ 12. Walter MG, Warren EL, McKone JR, Boettcher SW, Mi Q,
Santori EA, Lewis NS: Solar water splitting cells. Chem Rev
personal relationships that may be considered as po- 2010, 110:6446–6473.
tential competing interests: Ken Sakaushi reports 13. You B, Sun Y: Innovative strategies for electrocatalytic water
financial support was provided by Japan Science and splitting. Acc Chem Res 2018, 51:1571–1580.
Technology Agency. Ken Sakaushi reports financial 14. Chatenet M, Pollet BG, Dekel DR, Dionigi F, Deseure J, Millet P,
support was provided by Japan Society for the Promotion Braatz RD, Bazant MZ, Eikerling M, Staffell I, et al.: Water
electrolysis: from textbook knowledge to the latest scientific
of Science. strategies and industrial developments. Chem Soc Rev 2022,
51:4583–4762.
Data availability 15. Shinagawa T, Garcia-Esparza AT, Takanabe K: Insight on Tafel
* * slopes from a microkinetic analysis of aqueous electro-
Data will be made available on request. catalysis for energy conversion. Sci Rep 2015, 5, 13801.
This report insightfully discussed the theoretical description of the ki-
Acknowledgment netics of water electrocatalytic fundamental reactions based on
microkinetic analysis scribing the coverage-dependent Tafel slopes of
HW and KS are indebted to the National Institute for Materials Science for the reaction.
the support. This work was financially supported by JST-Mirai Program
Grant Number JPMJMI21EA, Japan. For KS, this work was partially 16. Tarasevich MR, Sadkowski A, Yeager E: Oxygen electro-
supported by JSPS KAKENHI Grant Number 21K18941, Japan. * * chemistry. In Comprehensive treatise of electrochemistry:
Volume 7 kinetics and mechanisms of electrode processes.
Edited by Conway BE, Bockris JOM, Yeager E, Khan SUM,
References White RE, Springer US; 1983:301–398.
Papers of particular interest, published within the period of review, This book presents the conprehensive summary for oxygen-related
have been highlighted as: electrochemical reactions.

* of special interest 17. Bockris JOM: Kinetics of activation controlled consecutive

* * of outstanding interest electrochemical reactions: anodic evolution of oxygen.
J Chem Phys 1956, 24:817–827.

1. Global-Energy-Perspective-2022. McKinsey & Company; 2022. 18. Bockris JOM, Otagawa T: Mechanism of oxygen evolution on
https://www.mckinsey.com/industries/oil-and-gas/our-insights/ * perovskites. J Phys Chem 1983, 87:2960–2971.
global-energy-perspective-2022. This report is a key paper to understand OER mechanism, which is the
study of electrode kinetic behaviour of the electrolytic evolution of
2. Mekala Krishnan HS, Woetzel Jonathan, Smit Sven, oxygen on the perovskites (ABO3).
Pacthod Daniel, Pinner Dickon, Nauclér Tomas, Tai Humayun,
Farr Annabel, Wu Weige, Imperato Danielle: The net-zero chal- 19. Fabbri E, Schmidt TJ: Oxygen evolution reaction—the enigma
lenge: accelerating decarbonization worldwide. McKinsey Sus- * in water electrolysis. ACS Catal 2018, 8:9765–9774.
tainability; 2022:224. https://www.mckinsey.com/capabilities/ This report is one of good summary for the issues on OER, which
sustainability/our-insights/the-net-zero-challenge-accelerating- presents the awareness among the scientific community devoted to
decarbonization-worldwide. progresses in water electrolyzers of the recently development.

3. Hydrogen for Net-Zero. In A critical cost-competitive energy 20. Sakaushi K, Uosaki K: Computationally empowered design of
vector. Hydrogen Council, McKinsey & Company; 2021. https:// emerging earth-abundant electrocatalysts toward electron-/
hydrogencouncil.com/en/hydrogen-for-net-zero/. proton-transferring energy conversion. Curr Opin Electrochem
2021, 26, 100661.
4. Kudo A, Miseki Y: Heterogeneous photocatalyst materials for
water splitting. Chem Soc 2009, 38:253–278. 21. Sakaushi K: Science of electrode processes in the 21st cen-
tury: fundamental understanding of microscopic mecha-
5. The sixth basic energy plan edited by: agency of natural nisms towards advancing electrochemical technologies. Bull
resources and energy of ministry of economy, trade and Chem Soc Jpn 2021, 94:2423–2434.
industry of Japan. https://www.enecho.meti.go.jp/category/
others/basic_plan/. Accessed 5 April 2022. 22. Man IC, Su H-Y, Calle-Vallejo F, Hansen HA, Martínez JI,
Inoglu NG, Kitchin J, Jaramillo TF, Nørskov JK, Rossmeisl J:
6. Trasatti S: Electrocatalysis: understanding the success of Universality in oxygen evolution electrocatalysis on oxide
** DSA®. Electrochim Acta 2000, 45:2377–2385. surfaces. ChemCatChem 2011, 3:1159–1165.
This work is historical overview on the development of DSA through of
the past over 70 years of electrochemistry. 23. Wang Q, Dastafkan K, Zhao C: Design strategies for non-
precious metal oxide electrocatalysts for oxygen evolution
7. Grotheer M, Alkire RC, Varjian R, Srinivasan V, Weidner JW: reactions. Curr Opin Electrochem 2018, 10:16–23.
Industrial electrolysis and electrochemical engineering.
Electrochem Soc Interface 2006, 15:52–54. 24. Wu Z-P, Lu XF, Zang S-Q, Lou XW: Non-noble-metal-based
* electrocatalysts toward the oxygen evolution reaction. Adv
8. De Nora O: Anwendung maßbeständiger aktivierter Titan- Funct Mater 2020, 30, 1910274.
** Anoden bei der Chloralkali-Elektrolyse. Chem Ing Tech 1970, This report presents the review on the current states, challenges, and
42:222–226. perspectives for non-noble-metal-based OER electrocatalysts.
This report is one of the first studied on dimensionally stable anodes or
DSA. 25. Xie X, Du L, Yan L, Park S, Qiu Y, Sokolowski J, Wang W, Shao Y:
Oxygen evolution reaction in alkaline environment: material
9. Sakaushi K, Antonietti M: Carbon- and nitrogen-based organic challenges and solutions. Adv Funct Mater 2022, 32, 2110036.
frameworks. Acc Chem Res 2015, 48:1591–1600.
26. Shi Z, Wang X, Ge J, Liu C, Xing W: Fundamental under-
10. Sakaushi K, Antonietti M: Carbon- and nitrogen-based porous standing of the acidic oxygen evolution reaction: mechanism
* solids: a recently emerging class of materials. Bull Chem Soc study and state-of-the-art catalysts. Nanoscale 2020, 12:
Jpn 2014, 88:386–398. 13249–13275.

www.sciencedirect.com Current Opinion in Electrochemistry 2022, 36:101136

12 Fundamental & Theoretical Electrochemistry (2022)

27. Yang Y, Peltier CR, Zeng R, Schimmenti R, Li Q, Huang X, Yan Z, 45. Tamura H, Iwakura C: Metal oxide anodes for oxygen evolu-
Potsi G, Selhorst R, Lu X, et al.: Electrocatalysis in alkaline tion. Int J Hydrogen Energy 1982, 7:857–865.
media and alkaline membrane-based energy technologies.
Chem Rev 2022, 122:6117–6321. 46. McCrory CC, Jung S, Peters JC, Jaramillo TF: Benchmarking
* * heterogeneous electrocatalysts for the oxygen evolution re-
28. Spöri C, Kwan JTH, Bonakdarpour A, Wilkinson DP, Strasser P: action. J Am Chem Soc 2013, 135:16977–16987.
The stability challenges of oxygen evolving catalysts: to- This report presents the detailly procedure for evaluating the activity,
wards a common fundamental understanding and mitigation stability, and electrochemically active surface area for heterogeneous
of catalyst degradation. Angew Chem Int Ed 2017, 56: OER catalysts under standard conditions.
5994–6021.
47. McCrory CCL, Jung S, Ferrer IM, Chatman SM, Peters JC,
29. Hu C, Zhang L, Gong J: Recent progress made in the mech- Jaramillo TF: Benchmarking hydrogen evolving reaction and
anism comprehension and design of electrocatalysts for oxygen evolving reaction electrocatalysts for solar water
alkaline water splitting. Energy Environ Sci 2019, 12: splitting devices. J Am Chem Soc 2015, 137:4347–4357.
2620–2645.
48. Lee Y, Suntivich J, May KJ, Perry EE, Shao-Horn Y: Synthesis
30. Wei C, Rao RR, Peng J, Huang B, Stephens IEL, Risch M, Xu ZJ, and activities of rutile IrO2 and RuO2 nanoparticles for
* Shao-Horn Y: Recommended practices and benchmark ac- oxygen evolution in acid and alkaline solutions. J Phys Chem
tivity for hydrogen and oxygen electrocatalysis in water Lett 2012, 3:399–404.
splitting and fuel cells. Adv Mater 2019, 31, 1806296.
This report reviewed the details for the electrochemical cell setup, 49. Pfeifer V, Jones TE, Wrabetz S, Massué C, Velasco Vélez JJ,
measurements, and data analysis used to quantify the kinetics of the Arrigo R, Scherzer M, Piccinin S, Hävecker M, Knop-Gericke A,
HER, HOR, OER, and ORR in acidic and basic solutions. et al.: Reactive oxygen species in iridium-based OER cata-
lysts. Chem Sci 2016, 7:6791–6795.
31. Huang Z-F, Song J, Dou S, Li X, Wang J, Wang X: Strategies to
break the scaling relation toward enhanced oxygen electro- 50. Cherevko S, Geiger S, Kasian O, Kulyk N, Grote J-P, Savan A,
catalysis. Matter 2019, 1:1494–1518. Shrestha BR, Merzlikin S, Breitbach B, Ludwig A, et al.: Oxygen
and hydrogen evolution reactions on Ru, RuO2, Ir, and IrO2
32. Lei Z, Wang T, Zhao B, Cai W, Liu Y, Jiao S, Li Q, Cao R, Liu M: thin film electrodes in acidic and alkaline electrolytes: a
Recent progress in electrocatalysts for acidic water oxida- comparative study on activity and stability. Catal Today 2016,
tion. Adv Energy Mater 2020, 10, 2000478. 262:170–180.
33. Gao L, Cui X, Sewell CD, Li J, Lin Z: Recent advances in acti- 51. Comninellis C, Vercesi GP: Characterization of DSA®-type
vating surface reconstruction for the high-efficiency oxygen * oxygen evolving electrodes: choice of a coating. J Appl
evolution reaction. Chem Soc Rev 2021, 50:8428–8469. Electrochem 1991, 21:335–345.
This report discussed on the influence of the selection of coating ma-
34. Ding H, Liu H, Chu W, Wu C, Xie Y: Structural transformation terials on the performance of OER, which is useful tool for development
of heterogeneous materials for electrocatalytic oxygen evo- of DSA.
lution reaction. Chem Rev 2021, 121:13174–13212.
52. Krýsa J, Kule L, Mráz R, Rou
sar I: Effect of coating thickness
35. Lyu F, Wang Q, Choi SM, Yin Y: Noble-metal-free electro- and surface treatment of titanium on the properties of IrO2-
catalysts for oxygen evolution. Small 2019, 15, 1804201. Ta2O5 anodes. J Appl Electrochem 1996, 26:999–1005.
36. Kim JS, Kim B, Kim H, Kang K: Recent progress on multimetal 53. Kim Y, Jin D, Lee C, Lee Y: Iridium-copper oxide nanotubes
oxide catalysts for the oxygen evolution reaction. Adv Energy catalyzing pH-universal oxygen evolution reaction with
Mater 2018, 8, 1702774. highly improved activity and durability via elemental substi-
tution. J Alloys Compd 2022, 909, 164813.
37. Hong WT, Risch M, Stoerzinger KA, Grimaud A, Suntivich J,
Shao-Horn Y: Toward the rational design of non-precious 54. Hubert MA, Gallo A, Liu Y, Valle E, Sanchez J, Sokaras D,
transition metal oxides for oxygen electrocatalysis. Energy Sinclair R, King LA, Jaramillo TF: Characterization of a dynamic
Environ Sci 2015, 8:1404–1427. Y2Ir2O7 catalyst during the oxygen evolution reaction in acid.
J Phys Chem C 2022, 126:1751–1760.
38. Danilovic N, Subbaraman R, Chang K-C, Chang SH, Kang YJ,
* Snyder J, Paulikas AP, Strmcnik D, Kim Y-T, Myers D, et al.: 55. Etzi Coller Pascuzzi M, Hofmann JP, Hensen EJM: Promoting
Activity–stability trends for the oxygen evolution reaction on oxygen evolution of IrO2 in acid electrolyte by Mn. Electrochim
monometallic oxides in acidic environments. J Phys Chem Acta 2021, 366, 137448.
Lett 2014, 5:2474–2478.
This work reported the surface-science approach to establish a rela- 56. Edgington J, Schweitzer N, Alayoglu S, Seitz LC: Constant
tionship between activity and stability of monometallic oxides during change: exploring dynamic oxygen evolution reaction
the OER reaction. catalysis and material transformations in strontium zinc
iridate perovskite in acid. J Am Chem Soc 2021, 143:
39. Rossmeisl J, Logadottir A, Nørskov JK: Electrolysis of water on 9961 – 9971.
(oxidized) metal surfaces. Chem Phys 2005, 319:178–184.
57. Rodríguez-García I, Galyamin D, Pascual L, Ferrer P, Peña MA,
40. Trasatti S: Electrocatalysis by oxides — attempt at a unifying Grinter D, Held G, Abdel Salam M, Mokhtar M, Narasimharao K,
approach. J Electroanal Chem Interfacial Electrochem 1980, et al.: Enhanced stability of SrRuO3 mixed oxide via mono-
111:125–131. valent doping in Sr1-xKxRuO3 for the oxygen evolution reac-
tion. J Power Sources 2022, 521, 230950.
41. Trasatti S: Electrocatalysis in the anodic evolution of oxygen
* * and chlorine. Electrochim Acta 1984, 29:1503–1512. 58. Miao X, Zhang L, Wu L, Hu Z, Shi L, Zhou S: Quadruple
This work established the one of the original volcano curve of elec- perovskite ruthenate as a highly efficient catalyst for acidic
trocatalytic activity in OER at various oxide electrodes as a function of water oxidation. Nat Commun 2019, 10:3809.
the enthalpy.
59. Grimaud A, Diaz-Morales O, Han B, Hong WT, Lee Y-L,
42. Reier T, Oezaslan M, Strasser P: Electrocatalytic oxygen * Giordano L, Stoerzinger KA, Koper MTM, Shao-Horn Y: Acti-
evolution reaction (OER) on Ru, Ir, and Pt catalysts: a vating lattice oxygen redox reactions in metal oxides to ca-
comparative study of nanoparticles and bulk materials. ACS talyse oxygen evolution. Nat Chem 2017, 9:457–465.
Catal 2012, 2:1765–1772. This work is the study on the activated lattice oxygen for OER and the
new reaction meachansim of OER in the catalytic surface site is also
43. Krishtalik LI: Kinetics and mechanism of anodic chlorine and
reported.
oxygen evolution reactions on transition metal oxide elec-
trodes. Electrochim Acta 1981, 26:329–337. 60. Haase FT, Bergmann A, Jones TE, Timoshenko J, Herzog A,
Jeon HS, Rettenmaier C, Cuenya BR: Size effects and active
44. Iwakura C, Hirao K, Tamura H: Anodic evolution of oxygen on
state formation of cobalt oxide nanoparticles during the
ruthenium in acidic solutions. Electrochim Acta 1977, 22:
oxygen evolution reaction. Nat Energy 2022, 7:765–773.
329–334.

Current Opinion in Electrochemistry 2022, 36:101136 www.sciencedirect.com

 Next-generation dimensionally stable electrodes Hoisang and Sakaushi 13

61. Stamenkovic VR, Strmcnik D, Lopes PP, Markovic NM: Energy 78. Che Q, Li Q, Chen X, Tan Y, Xu X: Assembling amorphous (Fe-
and fuels from electrochemical interfaces. Nat Mater 2017, 16: Ni)Cox-OH/Ni3S2 nanohybrids with S-vacancy and interfacial
57–69. effects as an ultra-highly efficient electrocatalyst: inner
investigation of mechanism for alkaline water-to-hydrogen/
62. Hammer B, Norskov JK: Why gold is the noblest of all the oxygen conversion. Appl Catal B 2020, 263, 118338.
metals. Nature 1995, 376:238–240.
79. Chen L, Ren X, Teng W, Shi P: Amorphous nickel-cobalt-
63. Vij V, Sultan S, Harzandi AM, Meena A, Tiwari JN, Lee W-G, borate nanosheet arrays for efficient and durable water
Yoon T, Kim KS: Nickel-based electrocatalysts for energy- oxidation electrocatalysis under near-neutral conditions.
related applications: oxygen reduction, oxygen evolution, Chem Eur J 2017, 23:9741–9745.
and hydrogen evolution reactions. ACS Catal 2017, 7:
7196–7225. 80. Walanda DK, Lawrance GA, Donne SW: Hydrothermal MnO2:
This report presents the overview of nickel based-electrocatalyts on the synthesis, structure, morphology and discharge perfor-
various energy applications and the future outlook of the material is mance. J Power Sources 2005, 139:325–341.
also discussed.
81. Li A, Ooka H, Bonnet N, Hayashi T, Sun Y, Jiang Q, Li C, Han H,
64. Hunter BM, Gray HB, Müller AM: Earth-abundant heteroge- * * Nakamura R: Stable potential windows for long-term electro-
* neous water oxidation catalysts. Chem Rev 2016, 116: catalysis by manganese oxides under acidic conditions.
14120–14136. Angew Chem Int Ed 2019, 58:5054–5058.
This report presents the highlight the advantages and challenge of non- This work presents the outstanding 3d-metal OER catalysts which
noble heterogeneous catalysts for water splitting. exhibits superior activity and stability in strong acid-media.
65. Deng X, Tüysüz H: Cobalt-oxide-based materials as water 82. Li A, Kong S, Guo C, Ooka H, Adachi K, Hashizume D, Jiang Q,
oxidation catalyst: recent progress and challenges. ACS * * Han H, Xiao J, Nakamura R: Enhancing the stability of cobalt
Catal 2014, 4:3701–3714. spinel oxide towards sustainable oxygen evolution in acid.
Nat Catal 2022, 5:109–118.
66. Trotochaud L, Ranney JK, Williams KN, Boettcher SW: Solution- This work is a recent report of the remarkable OER electrocatalyst
* * cast metal oxide thin film electrocatalysts for oxygen evolu- which obtains long lifetime in acid by two orders of magnitude with
tion. J Am Chem Soc 2012, 134:17253–17261. maintaining the activity.
This work investigated the high electrocatalytic activity of binary metal
oxide thin film for OER catalysts and observed the in-situ tranformation 83. You J, Yao R, Ji W, Zhao Y, Wang Z: Research of high entropy
of metal oxide to redox active metal hydroxide/oxyhydroxide phases as alloys as electrocatalyst for oxygen evolution reaction.
active sites. J Alloys Compd 2022, 908, 164669.
67. Lawrence MJ, Kolodziej A, Rodriguez P: Controllable synthe- 84. Zhang J, Quast T, He W, Dieckhöfer S, Junqueira JRC, Öhl D,
sis of nanostructured metal oxide and oxyhydroxide mate- Wilde P, Jambrec D, Chen Y-T, Schuhmann W: In situ carbon
rials via electrochemical methods. Curr Opin Electrochem corrosion and Cu leaching as a strategy for boosting oxygen
2018, 10:7 – 15. evolution reaction in multimetal electrocatalysts. Adv Mater
2022, 34, 2109108.
68. Li X, Walsh FC, Pletcher D: Nickel based electrocatalysts for
oxygen evolution in high current density, alkaline water 85. Zhou P, Liu D, Chen Y, Chen M, Liu Y, Chen S, Kwok CT,
electrolysers. Phys Chem Chem Phys 2011, 13:1162–1167. Tang Y, Wang S, Pan H: Corrosion engineering boosting bulk
Fe50Mn30Co10Cr10 high-entropy alloy as high-efficient alka-
69. Schoen MAW, Calderon O, Randell NM, Jimenez-Villegas S, line oxygen evolution reaction electrocatalyst. J Mater Sci
Daly KM, Chernikov R, Trudel S: Local structural changes in Technol 2022, 109:267–275.
polyamorphous (Ni,Fe)Ox electrocatalysts suggest a dual-
site oxygen evolution reaction mechanism. J Mater Chem 86. Wei R, Zhang K, Zhao P, An Y, Tang C, Chen C, Li X, Ma X,
2021, 9:13252–13262. Ma Y, Hao X: Defect-rich FeCoNiPB/(FeCoNi)3O4-x high-
entropy composite nanoparticles for oxygen evolution reac-
70. Pan L, Wang Q, Li Y, Zhang C: Amorphous cobalt-cerium tion: impact of surface activation. Appl Surf Sci 2021, 549,
binary metal oxides as high performance electrocatalyst for 149327.
oxygen evolution reaction. J Catal 2020, 384:14–21.
87. Jiang S, Tian K, Li X, Duan C, Wang D, Wang Z, Sun H, Zheng R,
71. Grewe T, Deng X, Weidenthaler C, Schüth F, Tüysüz H: Design Liu Y: Amorphous High-entropy Non-precious metal oxides
of ordered mesoporous composite materials and their elec- with surface reconstruction toward highly efficient and du-
trocatalytic activities for water oxidation. Chem Mater 2013, rable catalyst for oxygen evolution reaction. J Colloid Interface
25:4926–4935. Sci 2022, 606:635–644.
72. Chen J, Li H, Pei Z, Huang Q, Yuan Z, Wang C, Liao X, 88. Duan C, Li X, Wang D, Wang Z, Sun H, Zheng R, Liu Y: Nano-
Henkelman G, Chen Y, Wei L: Catalytic activity atlas of ternary sized high entropy spinel oxide (FeCoNiCrMn)3O4 as a highly
Co–Fe–V metal oxides for the oxygen evolution reaction. active and ultra-stable electrocatalyst for the oxygen evolu-
J Mater Chem 2020, 8:15951–15961. tion reaction. Sustain Energy Fuels 2022, 6:1479–1488.
73. Chen J, Li H, Yu Z, Liu C, Yuan Z, Wang C, Zhao S, 89. Laha S, Lee Y, Podjaski F, Weber D, Duppel V, Schoop LM,
Henkelman G, Li S, Wei L, et al.: Octahedral coordinated Pielnhofer F, Scheurer C, Müller K, Starke U, et al.: Ruthenium
trivalent cobalt enriched multimetal oxygen-evolution cata- oxide nanosheets for enhanced oxygen evolution catalysis in
lysts. Adv Energy Mater 2020, 10, 2002593. acidic medium. Adv Energy Mater 2019, 9, 1803795.
74. Qian Y, Xu X, He Y, Lei L, Xia Y, Zhang X: A novel monoclinic 90. Masuko N: Oxygen evolving anode of titanium substrate.
metal oxide catalyst for oxygen evolution reactions in alka- Tetsu-To-Hagane 1991, 77:871–877.
line media. Inorg Chem Front 2022, 9:941–949.
91. Bockris JO, apos m, Shamshul Huq AKM, Taylor HS: The
75. Burke MS, Kast MG, Trotochaud L, Smith AM, Boettcher SW: mechanism of the electrolytic evolution of oxygen on plat-
Cobalt–iron (Oxy)hydroxide oxygen evolution electro- inum. Proc Math Phys Sci 1956, 237:277–296.
catalysts: the role of structure and composition on activity,
stability, and mechanism. J Am Chem Soc 2015, 137: 92. Conway BE, Salomon M: Electrochemical reaction orders:
3638–3648. applications to the hydrogen- and oxygen-evolution re-
actions. Electrochim Acta 1964, 9:1599–1615.
76. Burke MS, Zou S, Enman LJ, Kellon JE, Gabor CA, Pledger E,
Boettcher SW: Revised oxygen evolution reaction activity 93. Colic V, Pohl MD, Scieszka D, Bandarenka AS: Influence of
trends for first-row transition-metal (Oxy)hydroxides in the electrolyte composition on the activity and selectivity
alkaline media. J Phys Chem Lett 2015, 6:3737–3742. of electrocatalytic centers. Catal Today 2016, 262:24–35.
77. Gong M, Dai H: A mini review of NiFe-based materials as 94. Bockris JOM, Otagawa T: The electrocatalysis of oxygen
highly active oxygen evolution reaction electrocatalysts. evolution on perovskites. J Electrochem Soc 1984, 131:
Nano Res 2014, 8:23–39. 290–302.

www.sciencedirect.com Current Opinion in Electrochemistry 2022, 36:101136

14 Fundamental & Theoretical Electrochemistry (2022)

95. Kamat GA, Zamora Zeledón JA, Gunasooriya GTKK, Dull SM, efficient oxygen evolution catalysis in neutral electrolyte. Adv
Perryman JT, Nørskov JK, Stevens MB, Jaramillo TF: Acid anion Mater 2018, 30, 1707522.
electrolyte effects on platinum for oxygen and hydrogen
electrocatalysis. Commun Chem 2022, 5:20. 107. Ge R, Ren X, Qu F, Liu D, Ma M, Hao S, Du G, Asiri AM, Chen L,
Sun X: Three-dimensional nickel–borate nanosheets array
96. Li N, Keane TP, Veroneau SS, Nocera DG: Role of electrolyte for efficient oxygen evolution at near-neutral pH. Chem Eur J
composition on the acid stability of mixed-metal oxygen 2017, 23:6959–6963.
evolution catalysts. Chem Commun 2020, 56:10477–10480.
108. Li R-Q, Hu P, Miao M, Li Y, Jiang X-F, Wu Q, Meng Z, Hu Z,
97. Zaffran J, Stevens MB, Trang CDM, Nagli M, Shehadeh M, Bando Y, Wang X-B: CoO-modified Co4N as a hetero-
Boettcher SW, Caspary Toroker M: Influence of electrolyte structured electrocatalyst for highly efficient overall water
cations on Ni(Fe)OOH catalyzed oxygen evolution reaction. splitting in neutral media. J Mater Chem 2018, 6:
Chem Mater 2017, 29:4761–4767. 24767 – 24772.
98. Garcia AC, Touzalin T, Nieuwland C, Perini N, Koper MTM: 109. Surendranath Y, Kanan MW, Nocera DG: Mechanistic studies
Enhancement of oxygen evolution activity of nickel * * of the oxygen evolution reaction by a cobalt-phosphate
oxyhydroxide by electrolyte alkali cations. Angew Chem Int catalyst at neutral pH. J Am Chem Soc 2010, 132:
Ed 2019, 58:12999–13003. 16501–16509.
This work presents one of the original OER mechanism at neutral pH.
99. Ding C, Zhou X, Shi J, Yan P, Wang Z, Liu G, Li C: Abnormal
effects of cations (Li+, Na+, and K+) on photoelectrochemical 110. Surendranath Y, Dincǎ M, Nocera DG: Electrolyte-dependent
and electrocatalytic water splitting. J Phys Chem B 2015, 119: electrosynthesis and activity of cobalt-based water oxidation
3560–3566. catalysts. J Am Chem Soc 2009, 131:2615–2620.
100. Görlin M, Halldin Stenlid J, Koroidov S, Wang H-Y, Börner M, 111. Kanan MW, Nocera DG: In situ formation of an oxygen-
Shipilin M, Kalinko A, Murzin V, Safonova OV, Nachtegaal M, evolving catalyst in neutral water containing phosphate and
et al.: Key activity descriptors of nickel-iron oxygen evolution Co2+. Science 2008, 321:1072–1075.
electrocatalysts in the presence of alkali metal cations. Nat
Commun 2020, 11:6181. 112. Bediako DK, Surendranath Y, Nocera DG: Mechanistic studies
of the oxygen evolution reaction mediated by a nickel–borate
101. Suntivich J, Perry EE, Gasteiger HA, Shao-Horn Y: The influ- thin film electrocatalyst. J Am Chem Soc 2013, 135:
ence of the cation on the oxygen reduction and evolution 3662–3674.
activities of oxide surfaces in alkaline electrolyte. Electro-
catalysis 2013, 4:49–55. 113. Dresp S, Dionigi F, Klingenhof M, Strasser P: Direct electrolytic
splitting of seawater: opportunities and challenges. ACS
102. Rao RR, Huang B, Katayama Y, Hwang J, Kawaguchi T, Energy Lett 2019, 4:933–942.
Lunger JR, Peng J, Zhang Y, Morinaga A, Zhou H, et al.: pH- and
cation-dependent water oxidation on rutile RuO2(110). J Phys 114. Dresp S, Dionigi F, Loos S, Ferreira de Araujo J, Spöri C,
Chem C 2021, 125:8195–8207. Gliech M, Dau H, Strasser P: Direct electrolytic splitting of
seawater: activity, selectivity, degradation, and recovery
103. Li G-F, Divinagracia M, Labata MF, Ocon JD, Abel Chuang P-Y: studied from the molecular catalyst structure to the electro-
Electrolyte-dependent oxygen evolution reactions in alkaline lyzer cell level. Adv Energy Mater 2018, 8, 1800338.
media: electrical double layer and interfacial interactions.
ACS Appl Mater Interfaces 2019, 11:33748–33758. 115. Tong W, Forster M, Dionigi F, Dresp S, Sadeghi Erami R,
Strasser P, Cowan AJ, Farràs P: Electrolysis of low-grade and
104. Abe H, Murakami A, Tsunekawa S, Okada T, Wakabayashi T, saline surface water. Nat Energy 2020, 5:367–377.
Yoshida M, Nakayama M: Selective catalyst for oxygen evo-
lution in neutral brine electrolysis: an oxygen-deficient 116. Schmickler W, Trasatti S: Comment on “trends in the ex-
manganese oxide film. ACS Catal 2021, 11:6390–6397. change current for hydrogen evolution” [J. Electrochem.
Soc., 152, J23 (2005)]. J Electrochem Soc 2006, 153:L31.
105. Nishimoto T, Shinagawa T, Naito T, Takanabe K: Delivering the
full potential of oxygen evolving electrocatalyst by condi- 117. Zeradjanin AR, Grote J-P, Polymeros G, Mayrhofer KJJ:
tioning electrolytes at near-neutral pH. ChemSusChem 2021, A critical review on hydrogen evolution electrocatalysis: Re-
14:1554–1564. exploring the volcano-relationship. Electroanalysis 2016, 28:
2256–2269.
106. Zhang Y, Wu C, Jiang H, Lin Y, Liu H, He Q, Chen S, Duan T,
Song L: Atomic iridium incorporated in cobalt hydroxide for

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