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Recent advances in doped ruthenium oxides as

Cite this: J. Mater. Chem. A, 2021, 9,
high-efficiency electrocatalysts for the oxygen
15506 evolution reaction
Hainan Sun * and WooChul Jung

Rutile ruthenium oxide (RuO2) exhibits relatively high reactivity towards the oxygen evolution reaction (OER)
due to its moderate capacity to bind oxygen. Thus, RuO2 has been demonstrated as a benchmark
electrocatalyst for the anodic reaction of water splitting, especially in an acidic electrolyte. Nevertheless,
there is still much room to promote the OER catalytic activity and the operational stability of RuO2 to
fulfill the requirements of practical applications. Optimizing the composition of RuO2 by a simple doping
strategy can be considerably beneficial, with enhanced catalytic activity and excellent stability achieved
simultaneously. This review presents the recent progress in doped ruthenium oxides as high-efficiency
electrocatalysts for the OER, with various types of dopants and design strategies summarized as well.
Received 25th April 2021
Accepted 10th June 2021
Maps of OER performance outcomes, including activity and stability, are presented to demonstrate the
advantages of doping and to compare the different effects of various introduced metal elements. Special
DOI: 10.1039/d1ta03452a
attention is paid to a clearer understanding of triggering reaction mechanisms by a series of
rsc.li/materials-a characterizations. The remaining challenges and future research directions are also proposed.

a highly active Ir-based IrOx/SrIrO3 material aer surface

1. Introduction reconstruction exhibiting remarkable OER activity with over-
Much attention has been devoted to the electrochemical oxygen potentials of 270–290 mV to reach a current density of 10 mA
evolution reaction (OER), an anodic half-reaction of water cm
2 for 30 h in an acidic electrolyte.31 However, on the
electrolysis, which can be powered by renewable electricity economic side, the high cost and low abundance of Ir metal (the
sources and produce high-purity hydrogen effectively without rarest of platinum-group metals) greatly limit its large-scale use
emitting CO2.1–3 Highly active, stable, and cost-effective water in commercial water electrolysis.32,33
oxidation electrocatalysts are in strong demand to meet the The noble metal Ru is the least expensive alternative and
requirements of commercial water electrolysis.4,5 Despite suitable platinum-group metal (Ru: 845 $ per ounce, Pt: 1226 $
considerable efforts in the area of electrochemical water elec- per ounce, Pd: 2918 $ per ounce and Ir: 6750 $ per ounce).33–37
trolysis in aqueous electrolytes (i.e., alkaline, acidic, and neutral Moreover, according to the volcano theory reported by Nørskov
conditions) to date, one of the major challenges remaining for et al. RuO2 sits close to the top of the volcano among widely
water electrolysis is the design of high-performance (in terms of studied oxides (i.e., RuO2, IrO2, RhO2, PtO2, Co3O4, and Mn3O4),
both activity and stability) OER catalysts.5–12 High-performance suggesting the excellent potential of RuO2 as an ideal candidate
and cost-effective OER electrolytes that work with acidic and for the OER.21,38 However, in terms of electrochemical activity,
basic electrolytes can advance the development of proton there is still much room for improvement due to the space
exchange membrane (PEM) water electrolysis and alkaline between RuO2 and the volcano vertex. Compared to Ir-based
water electrolysis, respectively.5,13–20 catalysts, the RuO2 catalyst is more active but less stable.21
Currently, noble metal-based oxides, in particular Ir- and Ru- Thus, another issue to be overcome for RuO2 is its operational
based materials, are considered as the benchmark electro- stability. The unsatisfactory operational stability of Ru-based
catalysts due to their high current density and fast reaction oxides is mainly attributed to the poorer chemical stability
kinetics towards the OER.10,21,22 Recently, Ir-based materials with the transformation of Ru4+ into higher valence states
such as Ir-based oxides with a perovskite or pyrochlore structure (Rux>4) during the electrocatalytic reaction.21,22,33,39 Although
and Ir-based hybrid materials have been extensively studied as much effort has been devoted to developing effective design
active and relatively stable OER electrocatalysts under acidic strategies ultimately to improve the activity and stability of
conditions.10,11,23–30 For example, Jaramillo et al. reported these materials, their performance outcomes leave much room
for improvement before meeting the requirements for practical
Department of Materials Science and Engineering, Korea Advanced Institute of Science
applications. Therefore, designing high-performance and
and Technology (KAIST), Daejeon 34141, Republic of Korea durable RuO2-based catalysts for the OER is a great challenge.

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Among the widely used strategies to improve the OER

performance of RuO2-based catalysts, the introduction of alien
elements is the simplest and the most straightforward method
to achieve a synergistic effect and decrease the consumption of
noble metals, which can, in turn, reduce the cost of the catalyst
design process and improve the OER performance.21,34,40–43
Particularly, rst-row transition metals are frequently used as
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doping elements due to their unique characteristics of 3d

valence electrons, abundance in nature, and low cost
(Fig. 1).4,37,44–49 Doping or introducing alien elements can effi-
ciently tune the intrinsic electronic structure of catalysts,
modulate active sites, create defects, and trigger reaction
mechanism transformation.19,48,50–53 Of note, some ruthenium-
based solid-solution systems are also discussed in this review
to highlight the positive effects of introducing alien elements. Fig. 2 Schematic of parameters that improve the OER performance
capabilities of doped-RuO2 catalysts.
Solid solution systems (e.g., Cr0.6Ru0.4O2, with a calculated mass
ratio of Cr to Ru equal to 1 : 1.29 (ref. 54)) differ from traditional
doped systems containing only small amounts of dopants (e.g.,
Cu-doped RuO2, calculated mass ratio of Cu to Ru equal to strategy can also provide another channel for energy transfer in
1 : 10.65 (ref. 55)). Moreover, combined with nanostructure and the host, leading possibly to unique physicochemical proper-
morphology engineering, doped-RuO2 catalysts exhibit signi- ties. Furthermore, the rational incorporation of dopants can
cantly enhanced mass activity and operational stability, espe- favorably modulate and tune the electronic and electrocatalytic
cially in acidic electrolytes.56–59 This review presents doped properties.21,60 In addition to the electronic structure, other key
ruthenium oxides as effective electrocatalysts for the OER, in factors that determine the electrocatalytic performance capa-
which various types of dopants and key parameters that deter- bilities of doped-RuO2 catalysts are also considered, such as
mine the OER performance are summarized. OER performance active sites, oxygen/metal defects, the reaction mechanism
maps, including data on the activity and stability, are also transformation process, and the powder morphology/particle
provided to demonstrate the advantages of the doping strategy size (Fig. 2).21,60–63
and to compare the different effects by the various metal
elements introduced. Special attention is paid to clarify the
triggering reaction mechanism by a series of characterizations. 2.1 Modulating the electronic structure
Optimizing the composition by lattice doping is the simplest
and the most effective strategy to modulate the electronic
2. Doping-induced effects structure of the parent materials.60,64–68 Due to the differences in
the physical properties of host and foreign atoms, such as the
The incorporation of metal ions, especially 3d transition metal
ionic radius, valence state, and electronegativity, doping-
ions, can readily reduce the cost of RuO2-based catalysts. This
induced redistributions of the charge density and spin density
can effectively regulate the functional properties and modulate
the adsorption of reactants at specic sites.43,69–72 Therefore,
benecial doping-induced electronic effects on electrochemical
performance outcomes are very frequently discussed in the
literature.50–52,67,73–77
For example, the prominent problem related to RuO2 in
acidic electrolytes is its poor stability, mainly ascribed to the
oxidation of lattice oxygen from oxygen vacancies generated
during the OER process.5 Under this condition, Ru atoms are
more likely to be exposed on the surface and further oxidized to
soluble high-valence states (i.e. RuO4).61,78 Moreover, the
collapse and loss of the catalyst surface crystalline matrix can
lead to the typically observed decayed stability. When the
formation energy of oxygen vacancies is much higher than the
redox H2O/O2 energy, the formation of soluble Rux>4 derivatives
would be thermodynamically hindered. The introduction of
foreign elements by lattice doping is an effective strategy by
Fig. 1 Earth-abundance levels of first-row transition metals and their
which to tune the electronic structure and increase the localized
current prices. The related data are collected from the literature (ref. gap between the O 2p band centers and the Fermi level, which
44). in turn enhances the energy barrier of the lattice oxygen

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Fig. 3 (a) Schematic diagrams of the band structures of W0.2Er0.1Ru0.7O2
d and RuO2. (b) Calculated oxygen vacancy formation energy in
different positions with various types of catalysts. Wavelet transform-extended X-ray absorption fine structures of (c) RuO2 and (d) W0.2Er0.1-
Ru0.7O2
d. Reproduced with permission.70 Copyright 2020, Nature Publishing Group.

oxidation process and eventually prohibits the formation of comparison, in which a clearly increased level of the formation
oxygen vacancies.70,79,80 Based on this concept, the co-doping energy of the oxygen vacancy at the pyramid vertex of W0.2-
strategy was utilized to design the W0.2Er0.1Ru0.7O2
d catalyst Er0.1Ru0.7O2
d (2.29 eV) compared to that of RuO2 (0.67 eV) was
based on RuO2.70 Specically, the synergistically rationalized Ru observed (Fig. 3b). Compared to the parent oxide, the electronic
4d and O 2p orbitals in RuO2 were investigated using the density structure of W0.2Er0.1Ru0.7O2
d was changed by the charge
of states (DOS) concept with density functional theory (DFT) redistribution revealed by the wavelet transform for the Ru K-
calculations, revealing that the gap between the O 2p band edge extended X-ray absorption ne structure (Fig. 3c and d).
center and the Fermi level was clearly enlarged (Fig. 3a). In addition, the adsorption energies for oxygen intermediates
Furthermore, for a quantitative assessment of the dynamic were optimized. As a result, the W0.2Er0.1Ru0.7O2
d catalyst
complexity of the metal dissolution process in an acidic elec- exhibited a low overpotential of 168 mV to reach a current
trolyte, the oxygen vacancy formation energy was calculated for density of 10 mA cm
2 together with superior stability for 500 h

Table 1 Summary of the OER performance of doped-RuO2 catalysts

Tafel slope
Doping elements Morphology h10a (mV) (mV dec
1) Stability Electrolyte

Cr54 Fine powder 178 59 10 h @ h10 0.5 M H2SO4

Mn69 Sphere-like nanocrystals 158 43 5000 CV cycles 0.5 M H2SO4
Fe110 Ultrathin networked nanowires 230 N.A.b 1000 CV cycles 0.5 M H2SO4
Mn, Fe119 Prismatic block type 270 41 5 h @ 1.58 V 0.1 M HClO4
Co110 Ultrathin networked nanowires 200 N.A. N.A. 0.5 M H2SO4
Co91 Nano-rod like 169 49 50 h @ h10 0.5 M H2SO4
Co118 Hollow nanosheets 171 61 10 h @ h10 1 M KOH
Ni110 Ultrathin networked nanowires 220 N.A. N.A. 0.5 M H2SO4
Co, Ni120 Prismatic block type 280 32 5 h @ 1.58 V 0.1 M HClO4
Cu55 Hollow porous polyhedron 188 44 8 h @ h10 0.5 M H2SO4
Cu112 Ultrasmall nanoparticle 204 56 5.56 h @ 1.456 V 1 M KOH
Zn86 Bullet-like nanoparticle 179 37 20 h @ h10 0.5 M H2SO4
Ir121 Nanosheets 225 @ h0.1c 60 N.A. 0.05 M H2SO4
W, Er70 Ultra-thin nanosheets 168 67 500 h @ h10 0.5 M H2SO4
RuO2 (ref. 87) Ultra-thin nanosheets 199 54 6 h @ h10 0.5 M H2SO4
a
Here h10 represents overpotentials corresponding to 10 mA cm
2. b
N.A. represents data not available in the literature. c Here h0.1 represents
overpotentials corresponding to 0.1 mA cm
2.

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(catalyst loaded on carbon paper) in an acidic electrolyte (Fig. 8, conrming the generation of defects via the removal of Zn
9 and Table 1). species during the acid etching process. Remarkably, the opti-
mized catalyst shows a small overpotential of 179 mV to reach
2.2 Creating oxygen/metal defect a current density of 10 mA cm
2 in 0.5 M H2SO4 (Fig. 8). The
robust operational stability is demonstrated by a z10% over-
The intrinsic properties (physical and chemical properties) of
potential increase aer a continuous test for 20 h (Fig. 9).
materials can be effectively tailored by introducing defects.81–83
In addition to the introduction of oxygen vacancies into RuO2,
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Thus intrinsic bottlenecks can be broken and the electro-

the effects of Ru vacancies (metal defects) on the electrochemical
catalytic performance can be improved. However, elaborately
activity were also evaluated. Using the molten salt method, Zhao
controlling the defects, including oxygen and metal defects for
et al. synthesized an ultra-thin two-dimensional structure of
RuO2, is a challenging task.
RuO2 nanosheets with abundant defects.87 The rutile RuO2
Nanoscale oxides commonly show novel physical properties
structure with nano-polycrystalline characteristics was conrmed
compared to their bulk counterparts.56,84 Nanostructured cata-
by XRD and high-resolution STEM. In addition, the nano-grain
lysts with favorable porosity enable the efficient diffusion of gas
orientations were randomly distributed, indicating the bound-
reactants/products during the reaction process.56,85 Further-
aries in the nanosheet. Moreover, the abundant multiscale
more, the intrinsic activities can be improved when the defects/
defects existed in various forms, such as grain boundaries and
vacancies are involved in ultra-small nanoparticles. Ge et al.
dislocations (Fig. 4c). Importantly, a high density of Ru vacancies
combined nanostructural engineering with metal/anionic
was found in the polycrystalline structure (Fig. 4d–f), demon-
defect engineering to improve the OER performance in acidic
strating a great potential to change the local electronic structure
media.86 First, the substitution of Ru with Zn2+ can introduce
and thereby affect the OER performance.
oxygen vacancies and decrease the crystallinity of RuO2. Then,
the soluble Zn species can be selectively removed by an acid
treatment, which can further induce defects and reduce the
particle sizes. From the X-ray photoelectron spectra (XPS) of O 2.3 Tuning the reaction mechanism
1s, a new peak at 530.9 eV emerged in the modied RuO2 Generally, two OER reaction mechanisms are involved in acidic
sample, which was attributed to the formation of oxygen media: the adsorbate evolution mechanism (AEM) and the
vacancies (Fig. 4a). Furthermore, Bader charge analyses lattice oxygen mechanism (LOM), in which absorbed water
revealed a low charge density on oxygen atoms adjacent to an molecules and lattice oxygen are related to the production of
oxygen vacancy compared to that of lattice oxygen (Fig. 4b), oxygen gas, respectively.5,88

Fig. 4 (a) XPS spectra of UfD-RuO2/CC (defective) in the O 1s regions. (b) Bader charge analyses of UfD-RuO2/CC. The unit of the atomic charge
is
jej. Reproduced with permission.86 Copyright 2019, Wiley-VCH. (c and d) STEM images of the RuO2 nanosheets. (e) The corresponding
atomic models of (d). (f) Intensity profiles of the red lines in (d). Reproduced with permission.87 Copyright 2020, The Royal Society of Chemistry.

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The vacancy-induced reaction mechanism transformation between the LOM and AEM in their reaction steps, revealing
from AEM to LOM has been demonstrated in various materials, that the OER would preferentially incur participation of the
such as perovskite oxides and oxyhydroxides, which could oxygen vacancy site, possibly also avoiding the over-oxidation of
effectively break the scaling relationship associated with the Ru to a high valence state (e.g., soluble RuO4) (Fig. 5c). Addi-
AEM toward enhanced electrocatalytic activity.89 The activation tionally, as another descriptor to evaluate the OER performance,
of lattice oxygen can be attributed to the greater covalency of the the p-band center of oxygen was calculated, showing that
metal–oxygen bonds, a descriptor of the OER that can be Ru1
xCoxO2
x exhibited a higher energy shi of the p-band
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quantied by calculating the charge transfer gap between metal center towards the Fermi level due to the generation of oxygen
3d and oxygen 2p states.90 One effective strategy to trigger the vacancies caused by the introduction of Co ions. Thus, these
LOM is to create abundant oxygen vacancies with an optimized factors contributed to the clearly enhanced activity and stability
electronic structure, which can be realized by the doping of of the Co-doped RuO2 electrocatalyst.
alien elements into the parent oxide. For RuO2-based electro-
catalysts, Tian et al. designed a Co-doped RuO2 nanorod.91 By
creating abundant oxygen vacancies and modulating the elec- 2.4 Increasing active sites
tronic structure, the Co-doped RuO2 was found to follow
Surface catalytic active sites contribute to the overall activity of
a vacancy-related LOM (Fig. 5a, le) rather than the AEM
a catalyst to some extent.63,92,93 Ideally, the surface of a catalyst
(Fig. 5a, right). DFT calculations reveal that oxygen vacancy sites
should have a maximum number of stable and active sites for
generated by the substitution of the 6-coordinated Ru site are
a specic reaction. One of the key issues in electrocatalysis is to
dominant and mainly participate in the OER process compared
identify the actual active sites during the electrochemical reac-
to the oxygen vacancy sites formed by the substitution of the 5-
tion, which is critical to understand the underlying reaction
coordinated Ru site. Furthermore, to evaluate and compare the
mechanism and further to guide the design of advanced elec-
rate-determining step in the four-electron transfer OER process
trocatalysts.94–96 Optimizing the active sites usually involves
of the AEM and LOM, free energy diagrams of the two mecha-
combining the design strategies of tuning compositions/crystal
nisms are presented (Fig. 5b). There is a clear 0.24 eV energy gap
structures and modulating exposed crystal facets.1,2,4,61,63,97

Fig. 5 (a) LOM and AEM mechanisms for RuO2. (b) Intermediates for the LOM and AEM processes. (c) Free energy diagrams of the four reaction
paths of LOM and AEM. Reproduced with permission.91 Copyright 2020, Cell Press.

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On the one hand, active sites themselves can be introduced ¼ 5) with an energy barrier of 0.78 eV (Fig. 6c).55 Regarding the
by the incorporation of alien atoms, particularly for elements high-index facets, the highly unsaturated Ru site (CN ¼ 3) at the
commonly showing high catalytic activity.48,98,99 On the other corner acted as a more catalytically active site. The RuO2 (111)
hand, the doping process can also modify the electronic struc- surface (CN ¼ 3) simultaneously exhibited a moderate energy
tures and surface adsorption properties at the catalytic active barrier for different reaction intermediates (e.g., *OH, *O, and
sites that improve the electrocatalysis.39,69,100 For example, Mn- *OOH). Under OER conditions, highly unsaturated Ru sites
doped RuO2 showed consistent diffraction peaks with would be oxidized to 5-coordinated species. In a further
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commercial RuO2 (Fig. 6a), indicative of their identical phase oxidizing environment, the energy barrier of the rate-
structures.69 Aer doping with elemental Mn, the number of determining step for each branch reaction would gradually
surface available active sites was greatly increased, as conrmed decrease. Notably, the reaction starting from *O*O was most
by the enhanced values of the double-layer capacitance. In favorable, exhibiting a low free energy of 0.66 eV for the rate-
detail, the values of the electrochemically active surface area for determining step (Fig. 6c).
Mn-doped RuO2 were approximately 1.6 and 3.8 times higher A major challenge in improving the electrochemical activity
than the corresponding values for nano RuO2 and commercial lies in the exposed active sites. Single-atom catalysts (SACs)
RuO2 (Fig. 6b). This result demonstrated that the doping enable the exposure of all of the metal atoms on the catalyst
process could dramatically enhance the available surface active surface, making the efficiency of atomic utilization nearly
sites. 100%.103 Inspired by SACs, to increase the utilization efficiency
Unsaturated coordination sites are also important active of the active sites in RuO2-based catalysts, it is also necessary to
sites in various electrocatalytic reactions.63,101,102 The coordina- expose abundant and highly dispersed active sites to electro-
tion numbers of surface-active atoms are directly associated lytes and reactants. A general strategy to enhance the utilization
with their adsorption energy level.63 Particularly, unsaturated of reactive sites is to synthesize catalysts with a particulate
atoms with lower coordination numbers are more thermody- morphology and particle size, specically, building a nano-
namically unstable and active to adsorb different reaction structure type of morphology and reducing the particle
intermediates compared to coordinatively saturated ones. For size.56,64,104–107 Therefore, the controlled and rational synthesis of
the Cu-doped RuO2 catalyst, DFT calculations revealed that the nanosized RuO2-based catalysts with well-regulated nano-
rate-determining step of the four-electron path was the forma- structures is a universal method in the development of highly
tion of *OOH on RuO2 (110) at a coordination number of 5 (CN efficient electrocatalysts (Fig. 7a).

Fig. 6 (a) XRD patterns of Mn-doped RuO2 and nano RuO2. (b) Electrochemically active surface area values revealed from the linear fitting of the
scan rate. Reproduced with permission.69 Copyright 2020, American Chemical Society. (c) Free energy profile of the OER on (110) and (111)
surfaces of RuO2. Reproduced with permission.55 Copyright 2018, Wiley-VCH.

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Fig. 7 (a) Catalyst development strategy by increasing the number of active sites to improve the electrocatalytic activity.1 Schematic of the
design processes of (b) Co-doped RuO2. Reproduced with permission.91 Copyright 2020, Cell Press. (c) Cr-doped RuO2. Reproduced with
permission.54 Copyright 2019, Nature Publishing Group. (d) Cu-doped RuO2. Reproduced with permission.55 Copyright 2018, Wiley-VCH. (e) Ru/
Cu-doped RuO2. Reproduced with permission.112 Copyright 2018, Wiley-VCH. (f) Mn-doped RuO2. Reproduced with permission.69 Copyright
2020, American Chemical Society.

One-dimensional (1D) metal nanostructures have been templates, and the removal of the templates.111 Metal–organic
applied in various elds, such as energy storage and photo(- frameworks (MOFs) have been widely used as templates due to
electro)catalysis.108 According to their shapes and aspect ratios, their porous properties with adjustable morphologies and pore
materials with 1D metal nanostructures can be further classi- sizes, as well as their well-characterized crystalline architec-
ed into nanowires, nanorods, nanobelts, and nanotubes.109 tures, allowing the fabrication of advanced electrocatalysts.64,106
Thus, 1D nanostructures offer a distinct platform for modu- The porous structure (precursor) can be utilized to load Ru
lating and utilizing the physicochemical properties of metals to sources (Ru-doping process) as well as to prepare low-cost Ir-
enable various applications.108 Furthermore, ultrathin net- free catalysts (nal morphology) (Fig. 7b–f). For example, Lin
worked nanowires can act as catalytic hot-spots to improve the et al. selected MIL-101(Cr), a type of MOF material, as the
electrochemical performance compared to well-dened net- precursor owing to its high specic surface area of more than
worked nanowires, a capability attributed to the considerable 3000 m2 g
1 and large pore size of approximately 3.0 nm, which
accessible structural defects and grain boundaries of the former is favorable for the loading of Ru sources (Fig. 7c).54
structure. A controlled structure combined with a doping
strategy can jointly optimize the Gibbs free energy, increase the 3. Maps of performance
number of active sites, and modulate electronic structures.
With regard to RuO2-based materials, Wang et al. rationally 3.1 Catalytic activity
designed a 3d transition metal-doped ultrathin RuO2 network Conventionally, evaluations of catalytic activity for the OER are
by a wet-chemical method and a subsequent post-annealing conducted using a three-electrode electrochemical system,
treatment.110 Particularly, aer the rst step of the wet- specically with a working electrode, a counter electrode, and
chemical approach, Co-doped RuO2 showed a 2D networked a reference electrode.113 For an as-synthesized powder, the
framework without obvious aggregation through the intercon- working electrode is typically a glassy carbon electrode with
nection of nanowires from different directions with an average naturally dried catalyst ink. In addition, substrates (e.g., nickel
diameter of 2.1  0.3 nm. Aer a post-annealing process, the foam and carbon paper) with loaded catalysts can be employed
network-like morphology can be well maintained. as self-supporting working electrodes.114 The overpotential
The template-assisted method is a widely used method to corresponding to the current density per geometric area of 10
fabricate three-dimensional (3D) nanostructured catalysts. In mA cm
2 is one of the most frequently used parameters for
this case, three major steps are involved: the preparation of the activity evaluations and comparisons, being a metric associated
original templates, lling of the target precursors into the with a solar water-splitting device.115

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Herein, we summarize the trends according to the periodic catalysts discussed in this review are mainly utilized in acidic
table in the overpotentials of various catalysts in acidic and environments, achieving greatly improved intrinsic activities.
alkaline electrolytes, highlighting OER activities improved by
doping strategies (Fig. 8 and Table 1). Doped-RuO2 catalysts are
3.2 Operational stability
most frequently applied in a strong acidic medium (e.g., 0.5 M
H2SO4). The commercial RuO2 catalyst has an overpotential Though rutile-structured RuO2 exhibits higher activity than
value of 325 mV at a current density of 10 mA cm
2, while IrO2, the operational stability of RuO2 under a high oxidative
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doped-RuO2 catalysts show values of around 180 mV. Speci- potential remains the most salient issue to be improved. As
cally, an ultra-low overpotential of 158 mV was achieved by Mn reported in the literature, commercial RuO2 can only survive for
doping, making an improvement of about 150 mV. few hours in an acidic electrolyte (Fig. 9a).54,55,87 The polarization
The anodic reaction mechanisms for alkaline electrolysis curves of commercial RuO2 exhibit obvious decay of the current
(eqn (1.1)) and acidic electrolysis (eqn (1.2)) are different, as density aer 2000 cycles (Fig. 9b).69
described below. Moreover, both the diffusion coefficient and An electrochemical chronopotentiometry analysis at a given
ionic mobility of H+ (9.3  10
9 m2 s
1 and 36.23  10
4 cm2 current density is a widely used method to evaluate the opera-
V
1 s
1) are approximately 1.8-fold higher than that of OH
(5.3 tional stability of designed catalysts. Typically, the stability of
 10
9 m2 s
1 and 20.64  10
4 cm2 V
1 s
1).11 Therefore, the the catalyst is evaluated by the rotating disk electrode tech-
OER reaction kinetics in acidic media is faster than that in nique. As shown in Table 1 and Fig. 9c, doped-RuO2 can
alkaline media due to the higher proton transfer rate, leading to manifest a stable potential to obtain the xed current density
lower overpotentials. for a relatively long time compared to that of the commercial
RuO2 catalyst. For example, the Co0.11Ru0.89O2
d catalyst loaded
4OH
(aq) / 2H2O (l) + O2 (g) + 4e
[Eoa ¼ 0.40 V vs. SHE] (1.1) on a glassy carbon electrode showed stable OER performance
for at least 50 h, revealing the benecial effect of improving the
2H2O (l) / O2 (g) + 4H+ (aq) + 4e
[Eoa ¼ 1.23 V vs. SHE] (1.2) stability by doping.91 However, under highly oxidative condi-
tions and in corrosive electrolytes, ultra-long stability may be
In addition, for an industrial alkaline electrolyzer, commer- interrupted by physical detachment from the carbon substrate
cial electrode materials for the anode and cathode are or the accumulation of gas bubbles, leading to a potential (or
transition-metal-based electrocatalysts such as nickel-based current density) jump to a high (or low) value.122 In addition,
materials. On the one hand, the electrocatalytic activity and catalysts loaded on self-supported conductive substrates are
durability of transition-metal-based electrocatalysts reportedly oen used as a working electrode in evaluations of the opera-
exceed those of precious-metal-based materials.22,116,117 On the tional stability.123 For instance, W0.1Er0.2Ru0.7O2
d loaded on
other hand, the low cost of transition metals greatly reduces the carbon paper (mass loading: 0.33 mg cm
2) can maintain high
cost of hydrogen production. However, PEM water electrolysis performance in acidic media for 500 h.70
continues to rely on precious-metal-based electrocatalysts.10,27 It is also important to note that the introduction of a transi-
Decreasing the usage of noble metals is one of the main tion-metal into the lattice can lead to the potential problem of
research objectives. As discussed above, considerable effort has transition-metal leaching in electrolytes during electrochemical
been devoted to developing effective design strategies to reactions, especially under acidic reaction conditions, commonly
improve the intrinsic activity towards the acidic OER. The resulting in dramatic activity degradation. Therefore, it is a great
design principles and mechanism that are well-established in challenge to achieve exceptionally high activity and superior
alkaline solutions are also expected to be extended to the design operational stability simultaneously. It was reported that Co0.11-
of OER electrocatalysts in acids.19 Overall, the RuO2-based Ru0.89O2
d (350) exhibited good stability, which was

Fig. 8 Map corresponding to activity levels. Overpotentials of various doped-RuO2 and commercial RuO2 in acid and alkali environments (Co1
represents Co-doped RuO2 nanowires,110 Co2 represents (Ru-Co)Ox,118 Ruo represents ultra-thin RuO2 nanosheets,87 and Oo represents ultrafine
defective RuO2 nanoparticles.86 The other detailed information and corresponding references can be found in Table 1).

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Fig. 9 Maps corresponding to operational stability. (a) Chronopotentiometry tests of commercial RuO2 catalysts at different fixed current
densities.54,55,87 (b) LSV curves of the OER for commercial RuO2 before and after 2000 CV cycles.69 (c) Stability comparison of doped-RuO2
catalysts with different test models (Cu1 indicates that the testing electrolyte was an alkaline solution, W2 means a catalyst loaded onto glassy
carbon, W3 denotes a catalyst loaded onto carbon paper, and Ruo denotes a Ru vacancy. The other detailed information and corresponding
references can be found in Table 1).

demonstrated by the generally unchanged XPS spectra of Co and microscopy (TEM), are essential.126,127 When comparing with
Ru aer a stability test.91 However, it is difficult to distinguish peak positions of standard materials, the phase information
subtle surface changes by the XPS technique. Though high can be conrmed by an XRD analysis. Furthermore, according
operational stability was achieved by Co doping, it is still to Bragg's law, different lattice constants between an alien atom
encouraged to use more advanced techniques to track the surface and the host atom are closely related to the diffraction angle,
changes aer an electrochemical reaction. Moreover, it can be which can further determine the parameters of the crystal
found that dopants of Er and W can have a charge redistribution structures. For example, from the XRD patterns of metal-doped
effect among Er, W, Ru, and O, leading to a stable valence state of RuO2 powders, the major phase can be indexed to the rutile
Ru4+ during the reaction process. This implies no formation of RuO2 phase (Fig. 10a–c).69,91 Importantly, for a high content of
RuO4 (soluble derivatives) during the acidic OER. Moreover, the Co, the peaks that belong to RuO2 shi to higher angles,
doping method can suppress the dissolution level of Ru (0.22 and indicative of lattice shrinkage due to the successful incorpora-
0.38 mg for W0.1Er0.2Ru0.7O2
d and Ru0.7O2
d respectively; tested tion of Co atoms into the RuO2 crystal lattice (the ionic radii of
in 0.5 M H2SO4 at 10 mA cm
2 for 100 h via an ICP analysis in Ru4+ and Co3+ are 0.62 and 0.54 Å, respectively) (Fig. 10b).91
a solution state). W and Er are also found in the solution aer the TEM images provide information about the particle size and
OER. The relatively stable concentrations of these elements in the morphology of powders under study. Particularly, a high-
electrolyte also indicate a stable structure during the reaction.70 resolution TEM (HR-TEM) image can provide strong evidence
To meet the requirements of commercial devices, such as alka- for the formation of single-crystalline structures.128 For
line water splitting and acidic PEM water splitting, the stability of example, as revealed from TEM images, the Co-doped RuO2
doped-RuO2 catalysts remains a challenge to be addressed.6,124 powder showed a nano-like morphology with a length and
Cost factors and practical applications should also be considered diameter of z20 nm and z8 nm, respectively (Fig. 10d).91 The
when designing catalysts and conducting OER performance clearly calculated lattice fringes demonstrate the high crystal-
evaluations.4,125 linity of the Co-doped RuO2 powder, indicating the successful
doping of Co atoms into the lattice of RuO2 powder (Fig. 10e),
which is also conrmed here by a selected-area electron
4. Routes to establish the structure–
diffraction (SAED) image (Fig. 10f). In addition, corresponding
activity relationship fast Fourier transform patterns and high-angle annular dark-
4.1 Gleaning the phase structure eld scanning transmission electron microscopy can be
utilized to demonstrate the formation of a rutile RuO2 phase for
To conrm the successful doping of a specied element into the
a doped catalyst, further supporting the XRD characterization
lattice of RuO2, advanced characterization techniques, such as
ndings.
powder X-ray diffraction (XRD) and transmission electron

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Fig. 10 (a) Crystal structure of RuO2 (a unit cell). (b) XRD patterns of Co-doped RuO2 powders. Reproduced with permission.91 Copyright 2020,
Cell Press. (c) XRD patterns of Mn-doped RuO2 and nano RuO2 powders. Reproduced with permission.69 Copyright 2020, American Chemical
Society. TEM image (d), HR-TEM image (e), and SAED image (f) of Co-doped RuO2 powder. Reproduced with permission.91 Copyright 2020, Cell
Press.

It should also be noted that while these characterizations of vacuum environment (e.g., XPS and so XAS testing).126,133
the phase structure identication process cannot provide direct According to the absorption energy values of Mn-doped RuO2
information about the reaction mechanism, they offer a basic compared to those of reference materials, including pure RuO2
understanding for subsequent characterizations and analyses. and Ru foil, the oxidation state of Ru in Mn-doped RuO2 was
In addition, they are preconditions necessary to establish determined to be +3.8 (Fig. 11c and d).69 Furthermore, from
models for theoretical calculations. the tting results and obtained parameters, the decreased
overpotentials can also be attributed to the O–Mn–O–Ru–O
structure (Fig. 11e and f).
4.2 Understanding electronic structural changes aer
doping
Surface electronic structures are directly linked to the 4.3 In situ/operando tracking of dynamic changes
adsorption properties of surface active sites, and electronic Ex situ characterizations usually provide information about the
structures can be effectively modulated by the introduction of pre- and post-chemical states of electrocatalysts, though these
alien atoms. Accordingly, the surface chemical states should methods cannot always capture the stepwise reaction kinetics
be studied and compared.40,129 Ex situ XPS measurements and detect the existence of short-lived intermediates.134 There-
provide information about valence state changes before and fore, advanced in situ/operando techniques have been demon-
aer the doping process. For example, aer Mn doping, the strated as unique tools to track dynamic surface changes and
binding energy levels of Ru 3p and 3d are approximately 0.3 the reconstruction process.
and 0.4 eV, respectively, compared to that of nano RuO2, The use of bimetal rather than single-metal catalysts has
revealing considerably changed electronic structures due to been demonstrated to achieve remarkable performance
the doping effect (Fig. 11a).69 The multivalent state of Mn in improvements. For RuO2-based catalysts, the incorporation of
Mn-doped RuO2 was revealed by the positions of the peaks of the noble metal Ir combines the high activity of RuO2 and the
Mn 2p at approximately 641.9 and 653.7 eV, correspondingly good stability of IrO2. From the results of ex situ XPS and
including Mn6+ and Mn7+ (Fig. 11b). To obtain precise infor- electrochemical test, Ir stabilization was proposed through the
mation about the valence and coordination states of Ru, X-ray formation of a common valence band, preventing the gener-
absorption spectroscopy (XAS) is a powerful technique that ation of RuO42
. To overcome the shortcomings of conven-
can provide atomic information of catalysts under study, such tional XPS operational condition of an ultra-high vacuum and
as the valence state, coordination number, bond length, and to track the origin of the stabilizing inuence of Ir, the near-
degree of disorder.130–132 In particular, hard XAS measure- ambient-pressure XPS (NAP-XPS) technique provides a prom-
ments can be taken at a normal pressure rather than in a high ising route.135,136 The work reported by R. Savinova's group

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Fig. 11 High-resolution XPS spectra of (a) Ru 3p and (b) Mn 2p. (c) Mn L-edge XANES spectra. (d) The function between the absorption energy
and Ru oxidation state. (e) R space and corresponding fitting curves of (e) pure RuO2 and (f) Mn-doped RuO2. Reproduced with permission.69
Copyright 2020, American Chemical Society.

revealed that NAP-XAS provides unique information about (Fig. 12c) and p-band centers could also demonstrate
potential-dependent changes in the valence state and the a reduction of the free energy for the rate-determining step
degree of hydration of Ru.121 Under operation, rutile-type RuO2 aer Mn-doping.7
anodes gradually and irreversibly transform into a hydrous The reaction efficiency is greatly constrained by adsorption-
Ru(IV) oxide form, while Ir stabilizes Ru in the anhydrous rutile energy scaling relationships. Specically, the universal rela-
phase. Furthermore, by changing the photon energy, it was tionship of DG(*OOH) ¼ DG(*OH) + 3.2  0.2 eV is applied to
found that the core of the catalytic particles mainly consists of most catalyst surfaces.139 Thus, DG(*O)
DG(*OH) can be
an anhydrous Ru–Ir(IV) oxide phase, whereas the surface is used as a descriptor to predict the electrochemical activity of
represented by the Ir(IV) oxide, a hydrated form of the Ru(IV) the OER.89 For example, to study the effects of Ru vacancies on
oxide, and Ru in higher valence states, specically RuO3 and the OER activities of the RuO2 nanocrystal, possible locations
RuO4(s). This work supplied a general route to stable Ru-based of Ru vacancies on the O-terminated (110) and (100) surfaces
anodes by the stabilization of Ru in a rutile oxide against the of RuO2, which are the two most stable low-index facets, were
hydroxide phase. considered.87 Theoretical overpotentials were calculated to
assess the OER activity according to the scheme proposed by
4.4 Gaining theoretical insight Rossmeisl. From the two-dimensional volcano curve, the OER
activities for the defect-free (110) and (100) surfaces were
Theoretical calculations can provide an in-depth under-
severely limited by the generation of *OOH, in which the
standing of the reaction mechanism taking place on the
overpotentials for A1 and B1 were 0.82 and 0.79 V, respectively
catalyst surface.1,4,132,137 For the OER operated via the AEM
(Fig. 12d). However, the formation of a Ru vacancy on the
mechanism, there are three intermediates involved, including
surface of RuO2 could effectively weaken the binding energy of
*OH, *O, and *OOH.4,7 The OER kinetics is determined by the
*O relative to that of *OOH and thus improve the OER activity
rate-determining step, reected by the calculated potential-
(Fig. 12e). Therefore, theoretical calculations could provide
determining steps. The free energies of four elementary
more insights into the enhanced OER performance of the
steps at various potentials were calculated, as they can provide
RuO2 electrocatalyst.
an intuitive comparison.137,138 For example, the third step (the
In short, to establish the structure–activity relationship of
formation of *OOH) was determined to be the rate-
doped-RuO2 electrocatalysts is a complicated process,
determining step for both the RuO2 and Mn-doped RuO2
involving a basic understanding of the phase structure aer
catalysts.69 When the potentials reached 1.23 V, a lower free
the introduction of alien dopants, learning about electronic
energy of 0.18 V was found (Fig. 12a and b). Notably, for the
structural changes aer doping (especially by in situ/operando
input potential of 2.71 V, all steps of the Mn-doped RuO2 (101)
techniques), and using DFT calculations to disclose the rela-
surface were downhill, while the third step for the RuO2 (101)
tionship between the electronic structure and the electro-
surface remained the uphill step. In addition, other descrip-
catalytic behaviors.
tors such as d-band centers relative to the Fermi level

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Fig. 12 (a) OER process steps. (b) Free energy level of Mn-doped RuO2 and RuO2 at various potentials. (c) Calculated DOS and a diagram of the
corresponding bonding and antibonding formation process for Mn-doped RuO2 and RuO2. Reproduced with permission.69 Copyright 2020,
American Chemical Society. (d) OER theoretical limiting potential plot for different configurations of RuO2. (e) Schematic illustration of the origin
of the improved OER activity upon the introduction of a Ru vacancy. Reproduced with permission.87 Copyright 2020, The Royal Society of
Chemistry.

5. Summary and outlook capabilities, there remain many challenges related to this
method and its applications.
The recent development of doped-RuO2 as an OER catalyst is In addition to the lattice doping strategy, building hybrid
summarized in this review. The structure–activity relationship composites, especially those created by the in situ synthesis
is discussed from various aspects, such as in terms of the method, can more readily realize a synergistic effect clearly to
electronic structure, active sites, defects, reaction mechanism, achieve enhanced electrocatalytic activity compared to that by
and powder morphology. We provided OER performance maps single-component counterparts.48,59,85,99,140–143 For example,
to highlight much via a simple doping method. Although Zhang et al. designed a hybrid nanoparticle-containing metallic
doped-RuO2 catalysts exhibit enhanced OER performance Ru, RuO2, and carbon nanotubes, exhibiting remarkably high

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activity toward the OER aqueous electrolytes at all pH levels.144 Program (2017M3A7B4049547), and National R&D Program
In detail, the hybrid requires low overpotentials of 180, 270, and (2020M3H4A3105824) through the National Research Founda-
210 mV to obtain a current density of 10 mA cm
2 in acidic tion of Korea (NRF) funded by the Ministry of Science, ICT and
(0.5 M H2SO4), neutral (1.0 M PBS), and alkaline (1.0 M KOH) Future Planning. This research has been performed as a coop-
electrolytes, respectively. As a descriptor to predict the OER eration project of “Basic project (referring to projects performed
activity, the projected Ru-d and O-p band centers were applied with the budget directly contributed by the Government to
to explain the obviously enhanced activity. The surface Ru-d and achieve the purposes of establishment of Government-funded
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O-p band center on RuO2 shis negatively aer Ru doping, research Institutes)” and supported by the Korea Research
which contributes to the enhanced OER activity. Moreover, both Institute of Chemical Technology (KRICT) (KS2122-10).
RuO2 and Ru/RuO2 have superior conductivity, which facilitates
their intrinsic kinetics.
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