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Materials Chemistry A
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High entropy alloy electrocatalysts: a critical

Cite this: J. Mater. Chem. A, 2020, 8,
assessment of fabrication and performance
14844
† Taehyun Kwon, † Jinwhan Joo
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Gracita M. Tomboc, and Kwangyeol Lee *

Received 21st May 2020
Accepted 6th July 2020
DOI: 10.1039/d0ta05176d
rsc.li/materials-a
High entropy alloy nanoparticles (HEA NPs) have gained considerable interest as electrocatalysts toward
fuel cells and water electrolysis due to their remarkable durability and catalytic activity. The unique
properties of HEA-based electrocatalysts may arise from the synergy of the mixed elements in a single-
phase solid solution. Unfortunately, the details regarding the active catalytic sites and intrinsic activity of
such catalysts are still very vague since the focused investigation on the properties of HEA NPs has only
started recently. In this report, the progress of development of HEA NPs is critically reviewed to
determine the extent of potential of HEA-based electrocatalysts. Herein, we present the proposed
thermodynamic models that guide the design of HEA single-phase solid solution, followed by the
discussion of different synthetic strategies to fabricate HEA NPs. Computational studies and machine-
learning assisted tools are also presented to find the optimum catalyst composition and structure of HEA
NPs, which is necessary to further improve the catalytic performance of HEA-based electrocatalysts and
to gauge the relevance of structural factors such as strain effects, adsorption energies, and the
interparticle distance to the catalytic performance. We conclude this report by drawing attention to
future research directions on HEA NPs.

between water, oxygen and hydrogen, namely, the oxygen

1. Introduction evolution reaction (OER), oxygen reduction reaction (ORR), and
Green energy technologies of water electrolysis, fuel cells, and hydrogen evolution reaction (HER). At the current stage,
metal–air batteries are mostly driven by redox reactions precious Pt and noble-metal based oxides like RuO2 and IrO2

Department of Chemistry and Research Institute for Natural Sciences, Korea † These authors contributed equally.
University, Seoul 02841, Republic of Korea. E-mail: kylee1@korea.ac.kr

Dr Gracita M. Tomboc received Taehyun Kwon (M.S. 2017) is

her Bachelor's degree in Chem- currently pursuing his Ph.D.
ical Engineering from Adamson degree in inorganic chemistry
University in 2012. She became under the supervision of Prof.
a registered Chemical Engineer Kwangyeol Lee in the Depart-
by passing the licensure exami- ment of Chemistry, Korea
nation under the Republic of the University (South Korea). His
Philippines Professional Regu- current research interests are on
lation Commission in 2013. She the design of nanostructured
received her Master's and Ph.D. catalysts and their potential
degrees in Energy Science and applications in fuel cells, elec-
Technology from Myongji trolytic water splitting and CO2
University, Republic of Korea in conversion.
August 2019. She is currently working as a postdoctoral researcher
at Korea University. Her research interests include the advanced
materials processing of ideal electrode materials for electro-
chemical energy storage system applications such as super-
capacitors, the water splitting process, direct methanol fuel cells,
and hydrogen generation.

14844 | J. Mater. Chem. A, 2020, 8, 14844–14862 This journal is © The Royal Society of Chemistry 2020

Highlight
are the state-of-the-art catalysts for the ORR, HER, and OER,
judged by their outstanding catalytic activity, selectivity, and
long-term stability under extreme operating conditions.1–3 The
high cost and scarcity of noble metals, however, are the serious
roadblocks toward the wide application of these technologies.
Thus, a continuous effort has been focused on the design and
modication of non-noble metal-based catalysts to achieve the
catalytic activity and stability of noble metal-based ones.4–6
Although there has been a considerable advance in transition
metal-based catalysts, most of the non-noble catalysts, however,
still fall short of noble-metal based catalysts in terms of catalytic
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performances.
In contrast to conventional alloys, which are typically
composed of only one, two, or occasionally three elements, high
entropy alloys (HEAs) are dened as single-phase solid solu-
tions with at least ve principal elements, each with an atomic
concentration between 5% and 35%.7 The main advantage of
HEAs over bimetallic or trimetallic nanoparticles is the maxi-
mization of congurational entropy, which endows the resul-
tant materials with extraordinary physicochemical and
mechanical properties, such as promising resistance to wear,
oxidation and corrosion, remarkable temperature strength, and
excellent stability.8–12 In particular, the notable catalytic activity
and exceptional durability of HEAs make them highly desirable
materials for diverse applications including electrocatalysis.
The unique characteristics of HEAs have been ascribed to the
high-entropy effect with the increased number of constituents,
the distorted lattice, and the sluggish diffusion.13–17
HEAs can be classied into several groups including
precious metal HEAs, transition metal-based HEAs, refractory
HEAs (Ti, V, Cr, Nb, Mo, Hf, Ta, and W), low-density HEAs (Li,
Be, Mg, Al, Si, Sc, Ti, Zn, and Sn), ceramic HEAs (oxides, metal
diborides, and perovskites), and lanthanide HEAs (Dy, Gd, Lu,
Tb, Tm, and Y).18–20 In this report, we will only focus on the
progress of the rst two groups of HEAs as electrocatalysts; we
identify them as noble metal-based HEAs and non-noble metal-
based HEAs. The rst group includes noble metals like Ag, Au,
Jinwhan Joo (M.S. 2016) is
currently pursuing his Ph.D.
degree under the supervision of
Prof. Kwangyeol Lee at the Nano
Chemistry Laboratory, Depart-
ment of Chemistry, Korea
University (South Korea). His
research interests are on the
development of functional
nanomaterials for photo- and
electro-catalytic water splitting
and CO2 reduction.
This journal is © The Royal Society of Chemistry 2020
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Journal of Materials Chemistry A
Pd, Pt, Rh, Ru, and Ir, while the second group is based on
transition metals such as Co, Ni, Fe, Mn, Cr, and Mo, and with
the possible addition of Al. Importantly, non-noble HEAs could
minimize the cost and usage of noble metals; however, they can
only be considered as cost-effective alternative catalysts when
the employed synthetic routes do not induce higher cost.21–24
During the early years, synthesized HEAs were mostly bulk
solids with nanocrystalline or amorphous microstructures,
which is associated with the sluggish nucleation and growth
rates owing to the reduced diffusion and interaction among the
inter-diffusing species during partitioning.25 HEA nanoparticles
(NPs) would offer benecial properties for electrocatalytic
applications, including a large surface area with many catalyt-
ically active sites, high material utilization efficiency, and
nanoscale size effects.26,27 However, combining ve or more
metal species into one nanostructured phase is not an easy
task.28 Therefore, enormous efforts to develop synthetic strate-
gies for the fabrication of HEA NPs have been made over the
past few years.
Initially, some of the thermodynamic models proposed to
guide the design of bulk HEAs are briey discussed to identify
the conditions required to form HEAs. Next, we present various
synthetic strategies to fabricate HEA NPs based on top-down,
bottom-up, and combinatorial approaches. The advantages and
limitations of each method are highlighted during the discus-
sion to overview the actual progress of the development of HEA
NPs. A short review of the catalytic performances of both noble
and non-noble metal based HEA NPs in various electrode
reactions in water electrolysers and fuel cells is also presented.
Note that the included relevant studies in this report were
carefully selected so that the term “HEA/s” always implies the
presence of a single solid solution phase with at least ve
principal elements. Also, to clearly indicate the major elements
(usually noble metal elements) for the electrocatalytic reaction,
we present the order of elements in HEA-based electrocatalysts
from large atomic number to small atomic number. Moreover,
the search for the optimum catalyst composition and structure
Professor Kwangyeol Lee ob-
tained his Ph.D. degree (1997) in
Chemistry from the University of
Illinois at Urbana – Champaign.
Aer fullling his military obli-
gation, he joined Korea Univer-
sity in 2003 as a chemistry
faculty member, before being
appointed as a professor. He is
the recipient of the Wiley-KCS
Young Scholar Award (2009,
Korean Chemical Society) and
the Excellent Research Award
(2019, KCS Inorganic Chemistry Division). His current interests
include the development of synthetic methodologies for nanoscale
materials and the development of nanotechnologies to support the
environment by creating sustainable energy.
J. Mater. Chem. A, 2020, 8, 14844–14862 | 14845

Journal of Materials Chemistry A
of HEA-based electrocatalysts through computational studies
and machine learning-assisted design of HEAs will be given due
attention. Finally, we conclude this report by summarizing the
recent advances in HEAs and drawing attention to the related
action items to point to the future research directions of HEA
NPs.
2. Synthetic strategies to fabricate
high-entropy alloys
HEAs tend to form a simple single-phase solid solution struc-
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ture, such as face-centred cubic (fcc) or body-centred cubic
(bcc), or a mixture of both.29,30 The formation of a single-phase
solid solution induces the unique properties of HEAs, such as
remarkable durability and catalytic activity. However, the
development of such complex, multicomponent alloys cannot
be accomplished by the simple mixing of various elements or
metals with an equal atomic ratio. In fact, the identication of
the specic combination of elements that leads to the forma-
tion of a single-phase HEA has been extremely difficult.
Herein, we briey summarized the earlier proposed criteria
that guide the design of bulk HEA single-phase solid solution
(Section 2.1). For a detailed discussion of the formation rules of
HEAs, readers may refer to previously reported excellent reviews
on this topic.13,31–34 Furthermore, the recently developed
synthetic methods to fabricate single-phase solid solution HEA
NPs will be discussed in Sections 2.2 and 2.3, along with the
discussion of the advantages and limitations of each method.
2.1. Synthesis of bulk HEAs
Following the classical thermodynamic description of Gibbs
energy of mixing of a solid solution phase, DGmix ¼ DHmix 
TDSmix, where DHmix is the mixing enthalpy, T is the tempera-
ture, and DSmix is the mixing entropy, several groups have
proposed certain rules to explain the formation of a single-
phase solid solution.34 For the random mixing of components,
Yeh et al. rst proposed a high entropy effect model.7 The
equation, derived from the congurational entropy of mixing, is
Pn
expressed as follows: DSmix ¼ R xi lnðxi Þ, where R is the gas
i¼1
constant and xi is the molar concentration.35 For an n-element
solution phase, the DSmix reaches its maximum, DSmix ¼ R ln(n),
when an equal molar concentration of each element is
consumed.35 Higher entropy of mixing leads to lower Gibbs
energy at constant temperature, allowing the solution phase to
be more stable. This perspective has been adopted by several
groups to form multicomponent alloys during the early years of
development of HEAs.36–39 However, the given criteria alone
were not sufficient to support the design of single-phase solid
solution HEAs. Zhang et al. discussed the solid solution
formation criteria for equiatomic ratio alloys, which include
a higher DSmix, atomic size difference (d) and mixing enthalpy.40
Fig. 1 shows the entropy of mixing of the equiatomic ratio alloys
as a function of the number of components, wherein the HEA
was characterized as an alloy that contains at least ve elements
with DSmix greater than 1.61R. In addition, they dened that the
14846 | J. Mater. Chem. A, 2020, 8, 14844–14862
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Fig. 1 The entropy of mixing of equiatomic ratio alloys as a function of
the number of the components.
atomic size difference, which is related to the size factor effect,
should be less than 4.6 (unitless), and the enthalpy of mixing
should be near zero of the absolute value, 2.685d  2.54 kJ
mol1 < DHmix < 1.28d + 5.44 kJ mol1, in order to facilitate the
formation of solid solution for multi-principle component
equiatomic alloys.35
The following parameters have been added as criteria to
design a single-phase HEA when Hume–Rothery rules for solid
solution formation are considered.41 The rst is electronega-
tivity (Dx), which is related to the electrochemical effect in the
HEA system, followed by the electron-to-atom ratio (e/a) and
valence electron concentration (VEC), which are both related to
the electron concentration effect. VEC is more useful in deter-
mining the phase stability of solid solutions. In particular, VEC
$ 8 will favour the formation of fcc-type solid solution, while
VEC < 6.87 tends to form a bcc-type solid solution.42,43 Recently,
Ye et al. proposed two new criteria which correlated the
enthalpy and entropy.7 The rst one includes two dimension-
less thermodynamic parameters, |SE|/SC  1  |HM|/TSC, where
SC denotes the congurational entropy of mixing for an ideal
gas, SE is the excessive entropy of mixing that is a function of
atomic packing, atom size and number of elements, HM is the
enthalpy of mixing and T is the temperature.44 The second
proposal involves a single dimensionless thermodynamic
property, which is expressed as f ¼ (SC  SH)/|SE|, wherein SH is
dened as the complementary entropy derived from the
enthalpy, |Ha|, and average melting point, Tm: SH ¼ |Ha|/Tm.
The group reported that the HEA would display a multi-phased
structure when f < fc (critical value), while a single-phase solid
solution is formed when f > fc.45
2.2. Synthesis of HEA nanoparticles
Since the advent of nanotechnology, intensive research efforts
have been directed toward the development of fabrication
methods for creating novel functional materials at the nano-
metre scale. The general properties of NPs, such as the size,
shape, crystallinity, and surface area, are dependent on the
synthetic strategy as well as experimental conditions.46 Thus, an
in-depth understanding of the synthetic approach is necessary
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to fabricate new materials with different physical and chemical
properties. The fabrication of NPs is classied into two major
categories, namely, top-down and bottom-up approaches. Table
1 summarizes the synthetic methods employed to fabricate
some of the most recent HEA NPs, based on the type of metal.
2.2.1. Top-down approach. The main advantage of the top-
down approach is the simplicity of the overall method. It
involves breaking down the solid material into smaller frag-
ments or particles with a size distribution of about 1 mm to 100
nm by applying a source of energy.47 The energy applied can be
mechanical, chemical, thermal, or laser irradiation. The major
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some of the commonly used top-down approaches to prepare
HEA-NPs.49–51
Mechanical alloying is a powder metallurgical processing
technique that involves repeated cold welding, fracturing, and
re-welding of blended powder particles in a high-energy ball
mill, and it is now widely used to prepare metastable and
advanced materials.52 High-energy ball milling is a widely known
technique, which stimulates the mechanical activation of the
powder mixture or induces the complete chemical reaction and
transformation of the powder reactants; the latter is oen used
to form nanocrystalline alloys using powder metallurgy.53 The

issues associated with this approach are the defective surface
chemistry and the drastic change in the physicochemical
properties of NPs.48 Mechanical alloying (ball milling and arc
melting), dealloying, laser ablation, and photolithography are
arc-melting technique can reach very high temperatures (4000

C) in a short period (10–20 seconds), which is advantageous for
the formation of a solid solution of multicomponent alloys.54
Dealloying involves dissolution and diffusion processes on
a rigid lattice to fabricate bulk nanoporous HEA materials.55 In

Table 1 Summary of the electrocatalytic ORR and MOR performance of high-entropy alloy-based catalysts

Synthetic
approach Material's category HEA composition Synthetic method Catalytic application Ref.

Top-down Noble PtIrOsRuCu Mechanical alloying (ball milling) & ORR, MOR 62
dealloying
IrMoNiCoAl Mechanical alloying (arc-melting) & OER, HER 63
dealloying
PtCuNiMnAl Mechanical alloying (melt-spinning) & ORR 28
dealloying
AuPtPdCuNiCoFeAl Mechanical alloying (arc-melting) & ORR, HER 64
dealloying
PtNiCoFeCr Mechanical alloying (arc-melting) — 26
PdNiCoFeCr
AuPtAgPdCu Mechanical alloying (arc-melting) & cryo- CO2RR 65
milling
AuAgCuNiCo Co-polymer lithography (SPBCL) a — 66
AuPtAgPdNiCo Co-polymer lithography (SPBCL) — 67
Non-noble CuNiCoFeCr Mechanical alloying (ball milling) — 68
TaMoNbVTi Mechanical alloying (arc-melting) & — 24
dealloying
CuNiCoFeCrAl Mechanical alloying (arc-melting) NH3 oxidation 7
CuNiCoFeCrAl Mechanical alloying (arc-melting) — 22
MoNiCoFeAl Mechanical alloying (arc-melting) & OER 14
NbNiCoFeAl dealloying
NiCoFeCrAl
NiCoFeMnCr Pulse laser ablation OER 69
Bottom-up Noble AuPtPdRhRu Wet-chemical synthesis (ultrasonication) HER 70
PtIrRhPdRu Solvothermal reaction — 60
PtPdCuNiCoFe Aerosol synthesis — 61
PdCuNiCoFe Electrodeposition MOR 71
PtLaNiCoFe Electro-shock reduction in nanosized OER, HER 72
droplets
PtAgCuNiCoFe Sputter deposition MOR 8
PtIrOsRhRu Inkjet printing & chemical reduction MOR 73
AuPtSnPdCuNiCoFe Carbothermal shock NH3 oxidation 74
PtPdNiCoFe Carbothermal shock ORR 75
IrWCeRuCuNiCoCr Carbothermal shock OER 76
Non-noble NiCoFeMnCr Combinatorial co-sputtering ORR 77
CuNiCoFeCr Wet-chemical synthesis (colloidal — 25
synthesis)
CuNiCoCrAl Sol–gel autocombustion — 78
NiCoFeMnMg Carbothermal shock — 79
a
SPBCL: Scanning probe block co-polymer lithography.

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Journal of Materials Chemistry A
the dealloying process, a less stable component is selectively
dissolved from a multicomponent alloy by using acidic or basic
chemicals. As the less noble metal is removed, the atoms of the
noble metals diffuse along the solid–liquid interface and re-
organize into a 3-dimensional network of pores/channels and
ligaments.47
Laser ablation is the discharge of macroscopic amounts of
materials from the surface of a solid, usually initiated by the
interaction of short-intense-laser pulses with the surface. It can
occur in a vacuum, gas, and liquid, provided that the gas or
liquid does not weaken the laser energy too much and that the
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light intensity on the solid surface is sufficient to keep the
material away from the equilibrium state.56 Photolithography
(PL), also termed as optical lithography or UV lithography, uses
light to transfer a geometric pattern from a photomask to
a photosensitive resist on the substrate. It involves an opera-
tional principle of exposing the material to electromagnetic
radiation to modify the solubility. The exposed photoresist is
immersed in solvents that dissolve the exposed (positive
photoresist) or unexposed (negative photoresist) regions to
provide access to the surface of the substrate. Pattern transfer is
achieved by an etching process.57
2.2.2. Bottom-up approach. Nanoparticle synthesis using
the bottom-up approach is based on the interaction of atoms or
some molecular species through a set of chemical reactions
provided by the technique.58 The precursor is typically a liquid
or gas that is ionized, dissociated, sublimed, or evaporated and
then condensed to form either an amorphous or a crystalline
nanoparticle.59–61 It is a facile method and exible in selecting
the molar concentration and feed rate of the reactant and
dispersant to obtain NPs with the desired size, shape, and pore
size distribution. The main advantage of the bottom-up
approach over the former method is the fabrication of NPs with
fewer surface defects, uniform chemical composition, and
narrower size distribution of about 100 nm to 0.1 nm.47 Wet
chemical synthesis, local thermal shock (carbothermal shock,
microwave-assisted, and ultrasonication), co-deposition from
multiple metal precursors (sputter-deposition, electrodeposi-
tion, and magnetron co-sputtering), and single-source
precursor strategies (sol–gel auto-combustion and single-source
precursor pyrolysis) are some of the bottom-up approaches
employed to fabricate HEA NPs.74,80–83
Hydrothermal and solvothermal processes describe a wet
chemical synthesis that relies on the solubility of the nano-
material under high pressure and temperature and is usually
implemented in a closed system. These methods are efficient in
controlling the grain size, particle morphology, crystalline
phase, and surface chemistry through regulation of the solution
composition, reaction temperature, pressure, solvent proper-
ties, additives, and aging time. Also, such techniques require
common equipment like a hot air oven and Teon-lined stain-
less-steel autoclave.84 Carbothermal shock (CTS) is a fast and
convenient method that efficiently prepare single-phase solid
solution HEA NPs.74 A typical CTS method involves the following
two-step process, ash heating and cooling of metal precursors
on oxygenated carbon supports, with adjustable shock dura-
tions and ramp rates. Rapid thermal decomposition of metal
14848 | J. Mater. Chem. A, 2020, 8, 14844–14862
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precursors at very high temperatures (2000 to 3000 K) forms
small liquid droplets of multi-metallic solutions while the
subsequent rapid cooling crystallizes these liquid droplets into
uniform and homogeneous alloy NPs without being subjected
to aggregation, element segregation, or phase separation.
Careful manipulation of CTS parameters like the shock dura-
tion, heating/cooling rates, temperature, and defect concen-
tration or alignment of carbon supports may lead to the
discovery of new HEA NPs with scientic signicance and
practical benets. The sputtering deposition process involves the
bombardment of a target surface with energetic gaseous ions
which initiate the physical ejection of surface atoms or small
clusters, followed by deposition in a medium like ionic liquids
to form NPs with uniform sizes.85 This technique is known as
a clean fabrication method of metal NPs since neither metal
precursors nor additional stabilizing agents are required to
generate highly stable NPs.86 Auto-combustion is a unique
method that uses energy from the exothermic decomposition of
a redox mixture of an organic compound with metal nitrates;
thus, it requires low initial temperature to activate the reaction.
A sol–gel auto-combustion method is a combination of chem-
ical gelation and ignition processes. The advantages of this
method are cost-effectiveness, simple preparation, and a gentle
chemistry route resulting in the formation of homogeneous,
nanosized particles.87–89
2.3. HEA nanoparticles based on material selection
2.3.1. Noble-metal based HEA nanoparticles. The synthesis
of HEA NPs via a ball milling process can be divided into two
experimental methods. The rst approach is commonly known
as mechanical alloying, wherein particular powders of required
elements are fed into a ball mill and milled until HEA phases
are formed.62,90 The second one involves the casting of HEA
ingots via ball milling at a temperature below 123 K, followed by
cryo-milling.91 The limitation of this method is that the mate-
rials are required to be particularly robust and ductile so that
cold welding can be feasible. However, cryo-milling offers many
advantages, including low contamination, reduced oxidation,
and suppressed recrystallization.92,93 Nellaiappan et al. fabri-
cated noble-metal based HEA NPs (AuPtAgPdCu), in which cast
HEAs were prepared via arc-melting, followed by cryo-milling to
obtain the nal products with an average size of 16  10 nm.65
The milling chamber was continuously purged using argon gas
to protect the powder from oxidation during milling, and the
cryo-mill ball was cooled down using liquid nitrogen. Atom
probe tomography (APT) conrmed the uniform distribution of
all elements at the atomic level in the single-phase fcc matrix.
Qui et al. combined traditional metallurgy, fast cooling, and
dealloying to synthesize senary AuPtPdCuNiAl and octonary
AuPtPdCuNiCoFeAl HEA NPs with ligament sizes of 2–3 nm and
equal elemental ratios.64 The composition of these HEAs was
precisely controlled through the dealloying process of the
designed precursor alloys. According to dealloying theory,
nanoporous noble metals such as Ir, Rh, Ru, Ag, Au, and Pt
could be easily incorporated into an Al-rich precursor alloy to
fabricate HEA NPs with a complex composition. Likewise, Jin
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et al. reported that by dealloying pre-designed Al-based
precursor alloys, it is possible to incorporate Ir metal with
another four metal elements (Al, Ni, Co, and X ¼ Mo, Nb, or V)
into one single nanostructured phase with a controlled
concentration of about z20 at% of Ir.63
Moreover, controlling the HEA particle size within the
nanoscale range is a difficult task, especially using conventional
dealloying approaches. Thus, synthesis methods that involve
full control over the particle size, elemental composition, and
phase are receiving enormous attention. Among these methods,
the CTS technique is the one being explored to prepare more
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chemical synthesis, which involves co-reduction of metal salts
along with capping agents that control crystal growth and
aggregation, or through CTS, which requires ash heating and
cooling of metal precursors on oxygenated carbon supports.74
The wet chemical synthesis technique was adopted by Singh
et al. to prepare CuNiCoFeCr HEA spherical NPs with an average
size of 26.7  3.3 nm.25 A typical laboratory reux set-up under
an argon atmosphere was utilized by the group to stimulate the
NP synthesis reaction. The selected area electron diffraction
(SAED) pattern revealed that the as-synthesized NPs possessed
an fcc structure as no diffraction signature corresponding to the

complex multi-metallic NP compositions.76 Yao et al. reported individual component metals and their oxides was obtained.
a two-step CTS method that employs ash heating and rapid Also, compositional analysis using scanning transmission
cooling of metal precursors on an oxygenated carbon support to electron microscopy – energy dispersive X-ray spectroscopy
synthesize HEA NPs with up to eight different metallic elements (STEM-EDX) of the NPs on a single nanoparticle level conrmed
(AuPtSnPdCuNiCoFe), with diameters of $5 nm.74 Flash heat- the uniform distribution of all the component elements within
ing at an extremely high temperature prompts the particle the NP volume.
‘ssion’ and ‘fusion’ that control the uniform mixture of Xu et al. fabricated quinary NiCoFeMnMg HEA NPs, which
multiple elements, while rapid cooling accelerates the kinetic were evenly distributed on super aligned electrospun carbon
rate to form single-phase solid solution NPs. Importantly, the nanobres (ACNFs) via a facile CTS method (Fig. 2a).79
shock duration, heating/cooling rates, temperature, and defect Compared with random carbon nanobers (CNFs), the ACNFs
concentration of carbon supports are critical parameters in the possessed a higher electron transport efficiency, which induced
CTS method, as these parameters have a direct effect on the a positive effect on accelerating the formation rate of HEA NPs,
HEA NP size, distribution, and structure.94
Similarly, scanning probe co-polymer lithography (SPBCL) is
a technique that uses the positional control offered by molec-
ular printing techniques to pattern single NPs on surfaces. The
principle behind the process of SPBCL is that it can deliver
1018 L volumes of polymers with metal ion precursors to the
desired location on a surface; the adjusted ratio of volume and
metal loading of the polymer feature can easily control the size
and composition of single-component particles.95,96 This
method takes advantage of polymer nanoreactors to conne
metal precursors at the nanoscale.97 In line with this, Chen et al.
evaluated the scope of this approach by synthesizing alloy NPs
with a combination of Au, Pt, Ag, Pd, Ni, and Co.67 The group
reported that the composition of the patterned alloy NPs could
be accurately controlled by optimizing the ink composition. In
particular, if the involved metals are miscible, a uniform atom
distribution and well-dened elemental ratio are possible.
However, if the metals are immiscible, phase-segregated binary
particles with a controlled size and composition are formed.98
On the other hand, alloy NPs prepared by the wet chemical
method are limited to three different metals, since the forma-
tion is mostly driven by enthalpy interactions among metallic
species. Recently, Liu et al. adopted an ultrasonication-assisted
wet chemical method to prepare a quinary AuPtPdRhRu HEA,
with z3 nm diameter.70 Notably, the acoustic cavitation
phenomenon during the ultrasonication process enabled the
generation of extremely high temperatures in localized micro-
scopic regions at momentary timespans (#109 s, z5000  C,
and 2000 atm), which is comparable to that of the CTS
method.99,100 Under these conditions, the group could fabricate Fig. 2 (a) HAADF-STEM image and elemental mapping analysis of
a NiCoFeMnMg HEA NP. (b) The direction of the CTS current is along
quinary HEA NPs via a wet chemical method, which is driven by
the fibres. (c) The direction of the CTS current is perpendicular to the
entropy maximization. fibres. (d) CTS for random carbon fibres. (e) The schematic diagram of
2.3.2. Non-noble metal-based HEA nanoparticles. Non- the CTS process. Reproduced with permission (ref. 79). Copyright
noble HEA NPs were previously synthesized by a facile wet 2020, Elsevier.

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 View Article Online

Journal of Materials Chemistry A Highlight

resulting in more uniform HEA NP coatings. Specically, the
relationship between the formation of HEA NPs and the direc-
tion of loaded current on the CNFs was investigated via a scan-
ning electron microscope (SEM), as shown in Fig. 2b–e. They
demonstrated that the HEA NPs were formed when the current
direction of the loaded electric pulse was along the bres and
not perpendicular. This nding is in agreement with the
signicant electrical conductivity anisotropy of the parallel
CNFs, which means that the electrons were easily transported
along the aligned bres.101,102 Using a similar CTS method, Xie
et al. synthesized a single solid-solution phase, quinary MoCu-
Published on 06 July 2020. Downloaded by Korea University on 8/6/2020 2:09:06 AM.
Meanwhile, the recent study of Waag et al. demonstrated
intriguing results regarding the single-step synthesis of
colloidal NiCoFeMnCr HEA NPs with diameters less than 5 nm
via a picosecond-pulsed laser ablation (PLA) technique
immersed in a ow cell (Fig. 3a–c).69 The PLA technique is
known as a top-down approach to give a wide-size distribution;
however, the generation of nanostructures by laser ablation can
become a bottom-up process represented by nucleation,
growth, and assembly of clusters from laser-ablated species.56
Fig. 3a shows the schematic illustration of the synthesis of HEA
NPs via the PLA method, wherein the initial step involves a laser

NiCoFe NPs, which surpassed the miscibility limitation in
bimetallic MoCo alloys.103 Importantly, according to the
prediction of high-entropy stabilized solid-solution in multi-
component alloys, the formation of HEAs usually requires the
atomic size difference (d) to be less than or equal to 4.6 and the
mixing enthalpy (DHmix) to be greater than 11.6 kJ mol1 but
less than 3.2 kJ mol1.104,105 In line with this, the group per-
formed atomic modelling of HEA NPs to calculate the related
parameters needed to assume the formation of a solid-solution
HEA. The results conrmed that the synthesized HEA-Mo45Co25
(Mo45Cu10Ni10Co25Fe10) NPs have a single solid solution phase
with only slight short-range chemical ordering. Furthermore,
the group showed that the MoCo-based HEA design could be
easily realized by simply varying the Mo/Co ratios.
beam irradiating the surface of the bulk HEA, followed by the
formation of cavitation bubbles by the ablation of hot atoms,
ions, and clusters from the bulk material. When the plume
cools, the ablated species condense. The collected condensates
were quenched, and they were released as NPs to the liquid
during the collapse of the cavitation bubble. The group sug-
gested that the ultrasmall NPs have originated from nucleation
and condensation in a low-density mixing region of the ablated
metal species. In particular, fast kinetics was assumed during
the cooling of the condensates with an estimated rate of 1012 K
s1, and that the surface passivation had suppressed the further
growth of nanoparticles.106,107
Furthermore, Niu et al. prepared a CuNiCoCrAl HEA through
sol–gel autocombustion.78 Sol–gel autocombustion is a fast and

Fig. 3 (a) Qualitative representation of the laser-based synthesis of HEA NPs; ultrashort-pulsed laser irradiation, the atomization/ionization of
the bulk, the subsequent nucleation/condensation of the ablated matter in the vapor phase, and the electrostatically stabilized colloidal HEA NPs.
(b) TEM image of NiCoFeMnCr HEA NPs and the electron diffraction pattern. (c) STEM image of NiCoFeMnCr HEA NPs and corresponding EDX
elemental mapping analysis. Reproduced with permission (ref. 69). Copyright 2019, Royal Society of Chemistry.

14850 | J. Mater. Chem. A, 2020, 8, 14844–14862 This journal is © The Royal Society of Chemistry 2020

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cost-efficient synthetic method used to fabricate nanosized
oxides via an exothermic reaction between oxidants and
fuel.108,109 The group utilized a nitrate–citric acid system as the
oxidant and fuel, respectively, with an optimal fuel-oxidant ratio
of 1 : 1. The synthesis of CuNiCoCrAl HEAs in the auto-
combustion process involved the formation of multicomponent
oxides derived from different metal oxides, followed by in situ
reductions to HEAs induced by reducing gases. The formation
of nanocrystalline HEAs was correlated with the chelation
between citric acid and metal ions; note that citric acid has
three carboxyl (–COOH) groups and one hydroxyl group (–OH),
Published on 06 July 2020. Downloaded by Korea University on 8/6/2020 2:09:06 AM.
which can provide four lone pair electrons to form a tetra-
dentate ligand.110 Aer the combustion process, fcc/bcc struc-
tured solid solutions with a grain size of 14 nm were obtained,
and the HEA nanoparticles showed a homogeneous distribu-
tion of metal ions without any interface.
Co-deposition by magnetron sputtering from several elemental
sources is a well-known technique for growing atomically mixed
materials.111 Löffler et al. synthesized a complex non-noble metal
alloy NiCoFeMnCr via a combinatorial co-sputtering method into
an ionic liquid (IL, [Bmim][(Tf)2N]).77 The advantage of sputtering
NPs into ILs is that only high-purity target elements or alloys are
present during the high-vacuum process.8 The IL served as
a suspension medium and stabilizer; thus, no surfactants are
needed to control the size of nanoparticles. TEM analysis deter-
mined the diameter of the NPs, which was about 1.7  0.2 nm.
Fast Fourier transform analysis showed that the as-deposited NPs
are amorphous with no reections, indicative of a crystalline
structure. At the same time, STEM-EDX veried the homogeneous
distribution of the ve elements in the NPs, which conrmed the
formation of single solid solution phase NPs induced by the high-
entropy effect.
On the other hand, Rekha et al. reported the synthesis of gra-
phene–HEA nanoparticle (CuNiCoFeCr) composites using the
combinatorial method involving mechanical milling and sonica-
tion assisted exfoliation.68 Mechanical milling of graphene and
metal powder was performed in the presence of a toluene medium,
followed by exfoliation of graphene via sonication in sodium lauryl
sulphate (SLS) solution. Aer sonication, the dispersion was sub-
jected to centrifugation at 8000 rpm to remove the SLS. The
centrifuged powder was then dispersed in ethanol and allowed to
settle, and then nally, the graphene–HEA nanoparticle compos-
ites were collected. Mechanical milling operation assisted the
incorporation of ne metal clusters within the spaces between the
graphite planes, while sonication produced HEA-nanoparticles
uniformly decorated on exfoliated graphene sheets.
A combination of PLA and inert gas condensation was
adopted by Bag et al. to synthesize advanced nanoparticulate
materials, including HEA–CuNiCoFeMn, with a complex
composition.112 Briey, a pico-second pulsed Yb:YAG (1030 nm)
laser was used for the ablation of different materials, which
were subsequently condensed in a He atmosphere to form
individual nanoparticles. The as-prepared nanoparticles are
transported from the growth/ablation zone using a forced gas
ow to be collected on a cold surface. The XRD pattern of HEA–
CuNiCoFeMn with the same elemental composition shows
a single fcc phase and an amorphous structure.
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Journal of Materials Chemistry A
3. High-entropy alloy nanoparticles
as electrocatalysts
3.1. Review of the catalytic performance of HEA NP-based
electrocatalysts
Because of the extraordinarily high corrosion-resistance due to
the entropy-driven stability of HEAs, HEA-based nanostructures
were utilized for various electrode reactions in fuel cells or water
electrolysers. In particular, Pt-based nanostructured HEAs
prepared by a chemical dealloying strategy have been utilized as
electrocatalysts for fuel cell electrode reactions such as the ORR
and the methanol oxidation reaction (MOR).
Li et al. investigated various quinary nanoporous Pt-based
HEAs as ORR electrocatalysts (Fig. 4).28 Nanoporous PtCuNiXAl
(np-PtCuNiXAl, X ¼ Mn, V, Co, Mo, Ti, Ir, Pd, and Au) materials
were prepared by chemical dealloying of a quinary mechanically
alloyed precursor, Pt1Cu1Ni1X1Al96, with 0.5 M NaOH solution.
Compared to ternary np-PtCuAl and quaternary np-PtCuNiAl,
the addition of the h element improved the ORR activity in
a 0.1 M HClO4 electrolyte (Fig. 4b and c). Among various
compositions, np-PtCuNiMnAl exhibited the highest ORR
activity, whose half-wave potential (0.945 VRHE) showed the
most positive value among the samples. The calculated mass
activity (Fig. 4d) of the np-PtCuNiMnAl catalyst was 3.5 A mgPt1
at 0.9 VRHE, which is about 16 times higher than that of
benchmark Pt/C catalysts (0.22 A mgPt1). Based on their DFT
calculation, the addition of Mn content decreased the energy
barrier of O2 / *OOH, which is the rate-determining step of the
ORR. Moreover, the np-PtCuNiMnAl catalyst exhibited excellent
durability, whose initial ORR activity retained its initial value
aer 30 000 potential cycles. Also, the np-PtCuNiMnAl catalyst
retained 91% of its initial activity aer 160 h operation at 0.7
VRHE (Fig. 4e). By their PXRD and STEM-EDX analysis, no
obvious element segregation was observed in np-PtCuNiMnAl
catalysts aer potential cycling. Similarly, nanoporous, senary
HEA catalysts exhibited superior electrocatalytic ORR activity
and stability, as Qiu et al. reported.64 The chemical dealloying of
the Au0.5Pt0.5Pd0.5Cu0.5Ni0.5Al97.5 alloy precursor was conducted
with 0.5 M NaOH solution, resulting in the formation of np-
AuPtPdCuNiAl. The np-AuPtPdCuNiAl catalyst exhibited
enhanced ORR activity, veried by the signicantly positively
shied half-wave potential (0.90 VRHE) compared to that of
benchmark Pt/C (0.82 VRHE). The mass activity of the np-
AuPtPdCuNiAl catalyst at 0.9 VRHE was evaluated to be 2.24 A
mgPt1, which is 10 times higher than that of Pt/C (0.22 A
mgPt1). Moreover, the np-AuPtPdCuNiAl catalyst retained
92.5% of its initial mass activity aer 100 000 potential cycles,
while the Pt/C catalyst retained 65% of its initial mass activity
aer 20 000 potential cycles. This excellent ORR durability of
HEA-based catalysts might have beneted from the high-
entropy stabilization effect, that is, the diffusion of atoms
during electrocatalysis is suppressed.13 In contrast, typical
binary Pt-based electrocatalysts undergo phase segregation or
catalyst dissolution during potential cycling.113–116
Because the incorporation of transition metal elements,
such as Cu and Ru, into Pt is one of the powerful tools to
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Journal of Materials Chemistry A
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Fig. 4 (a) HAADF-STEM image and EDX elemental mapping analysis of
the nanoporous PtCuNiMnAl catalyst. (b and c) ORR polarization
curves of the nanoporous HEA catalysts with different compositions in
O2-saturated 0.1 M HClO4 solution. (d) Comparison of Pt mass and
surface specific activities at 0.9 V vs. RHE. (e) Long term current–time
curve of the nanoporous PtCuNiMnAl for the ORR at 0.7 V vs. RHE.
Reproduced with permission (ref. 28). Copyright 2020, Elsevier.
fabricate a CO-tolerant surface,117,118 several Pt-based HEA
nanostructures were applied to the MOR. For example, Chen
et al. reported the fabrication and their electrocatalytic activity
toward the MOR of nanoporous PtIrOsRuCu (np-PtIrOsRuCu)
catalysts via chemical dealloying from a mechanically alloyed
PtIrOsRuCuAl precursor.62
The chemical dealloying process of mechanically alloyed
Al66Cu30(Pt44Ir5Os10Ru41)4 alloy powder was conducted in 1 M
HNO3 solution at room temperature, resulting in the formation
of np-PtIrOsRuCu, whose composition was revealed as 45.8%
Pt, 7.4% Ir, 11.6% Os, 19.2% Ru, and 16.0% Cu by EDX analysis.
The np-PtIrOsRuCu catalyst exhibited 3.7 times higher MOR
mass activity (857.5 mA mgPt1) than the benchmark Pt/C
catalyst (229.5 mA mgPt1) in a 0.5 M H2SO4 + 0.5 M CH3OH
electrolyte. The enhanced MOR activity of the np-PtIrOsRuCu
catalyst has originated from the CO-tolerant surface of HEA
composition, as veried by the ratio of forward anodic peak
current density (If) and backward anodic peak current density
14852 | J. Mater. Chem. A, 2020, 8, 14844–14862
View Article Online
Highlight
(Ib). The If/Ib ratio of np-PtIrOsRuCu was revealed to be 1.26,
which is higher than that of Pt/C (0.91), indicating the CO-
tolerant surface of Pt upon alloying with other metal elements.
The CO-tolerant surface of np-PtIrOsRuCu was also veried by
CO-stripping analysis, which exhibited a lower CO electro-
oxidation peak (130 mV negative than that of Pt/C). The CO-
tolerant surface of other HEA-based nanostructures was also
reported. Tsai et al. reported sputter deposition synthesis of
senary PtAgCuNiCoFe nanoparticles on gas diffusion electrodes
(GDEs) for the MOR under acidic conditions.36 The senary HEA
nanoparticle, whose composition is Pt50Ag8Cu10Ni11Co10Fe11,
exhibited higher anodic current density (504 mA mg1) than Pt
(451 mA mg1). Moreover, the If/Ib ratio of Pt50Ag8Cu10Ni11-
Co10Fe11 nanoparticles (1.09) exhibited a higher value than that
of Pt/C (0.88), indicating the CO-tolerant surface of HEA
composition.
Pd-based nanostructured-HEAs also exhibit electro-
catalytic activity toward the MOR under alkaline conditions.
Wang et al. reported the synthesis of quinary PdCuNiCoFe
alloy nanotube arrays (NTAs) by template-directed electro-
deposition.71 The PdCuNiCoFe NTAs showed two times
higher electrocatalytic mass activity (95 mA mgPd1) toward
the MOR than Pd NTAs in a 0.5 M NaOH + 0.5 M CH3OH
electrolyte. The promotion of the MOR activity of PdCuNi-
CoFe NTAs is attributed to the facile C–H bond cleavage and
formation of surface-binding hydroxyl species at a lower
potential, which is originated from the interactions between
Pd and other metals.119 This promotive effect of HEA forma-
tion is also supported by the X-ray photoelectron spectros-
copy (XPS) spectra of the catalysts. The Pd 3d peaks of
PdCuNiCoFe NTAs are positively shied (+2.35 eV) to the
higher region compared to those of Pd NTAs, which indicates
the alternation of the electronic state of Pd by strong electron
interactions with Cu, Ni, Co, and Fe components. The
performance of nanostructured HEA-based electrocatalysts
toward the ORR and MOR is summarized in Table 2.
On the other hand, the HER and OER are the two half-
reactions involved in electrocatalytic water splitting. These
hydrogen-based and oxygen-based alkaline electrochemical
reactions are oen hindered by sluggish kinetics, which
leads to a large overpotential and low round-trip effi-
ciency.120,121 Enormous effort has been devoted to the devel-
opment of highly efficient electrocatalysts for the HER and
OER based on the structure–activity relationship, to increase
the reaction rate and efficiency of the total system.121–123
Accordingly, Liu et al. reported AuPtPdRhRu alloy nano-
particles for HER application by an ultrasonication-assisted
wet chemical method (Fig. 5a and b).70 The as-synthesized
quinary AuPtPdRhRu nanoparticles on carbon (AuPtPdRhRu/
C), whose average diameter is 2.6  0.3 nm, exhibited excel-
lent HER activity and durability in a 1.0 M KOH electrolyte.
The required overpotential of AuPtPdRhRu/C to drive
a current density of 30 mA cm2 was 190 mV, which is
smaller than those of quaternary AuPtPdRh/C (260 mV) and
ternary AuPtRh/C (600 mV) catalysts. AuPtPdRhRu/C exhibi-
ted a lower Tafel slope of 62 mV dec1 compared to
AuPtPdRh/C (91 mV dec1), AuPtPd/C (177 mV dec1), and
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benchmark Pt/C (77 mV dec1) catalysts, indicating its

Ref.

64

62

28

75

62

71

36

38
superior activity toward the alkaline HER. Moreover,
AuPtPdRhRu/C exhibited stable electrocatalytic performance

0.5 M H2SO4 + 0.5 M

0.5 M H2SO4 + 0.5 M

0.5 M H2SO4 + 0.5 M

0.5 M NaOH + 0.5 M

over 8 h, veried by chronopotentiometry at a current density
of 100 mA cm2. Likewise, Qiu et al. reported noble-metal
free nanoporous HEA catalysts for the OER under alkaline
0.1 M HClO4

0.1 M HClO4

0.1 M HClO4
Electrolyte

conditions.124 Quinary nanoporous NiCoFeAlX (np-NiC-

1 M KOH

CH3OH

CH3OH

CH3OH

CH3OH
oFeAlX, X ¼ V, Cr, Mn, Cu, Zr, Nb, Mo) and senary np-
MoCuNiCoFeAl catalysts were fabricated by a mechanical
alloying and chemical dealloying strategy. Among the cata-
— 90.3% aer 10k cycles
73.1% aer 15k cycles

lysts, np-MoNiCoFeAl exhibited the lowest OER overpotential

92.5% aer 100k

— 100% aer 30k

(240 mV) to drive a current density of 10 mA cm2 in a 1.0 M

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— 71% aer 15 h
E1/2 (VRHE) If/Ib Durability test

KOH electrolyte. Moreover, the np-MoNiCoFeAl catalyst also

showed a smaller Tafel slope of 46 mV dec1, compared to
operation

ternary np-NiFeAl (62 mV dec1) and quaternary np-NiCoFeAl

cycles

cycles

(61 mV dec1). Moreover, the quinary np-MoNiCoFeAl

1.26 —

1.09 —

1.09 —

—
exhibited high durability compared to ternary and quater-
—

nary catalysts, and retained more than 95% of its initial

activity aer 2000 potential cycles. Due to the oxidative
0.945

potential under OER conditions, the surface of np-MoN-

0.86
0.9

0.9

iCoFeAl might undergo oxidation, forming surface oxides on

the HEA surfaces. Aer a chronopotentiometry test at 20 mA
cm2 for 50 h, however, the ve elements were still uniformly
Specic activitya (mA

distributed in np-MoNiCoFeAl, forming a high-entropy-oxide

(HEO) skin that exhibits high-entropy driven stability.
Summary of the electrocatalytic ORR and MOR performance of high-entropy alloy-based catalysts

@ 0.9 VRHE for the ORR; @ maximum current for the MOR. b A mgPt+Pd+Au1. c By CO-stripping. d A mgPd1.

While catalysts in alkaline electrolytes are required to

catalytically break the H–O–H bond before it can adsorb H+
cmPt2)

ions, available free H+ ions in acidic electrolytes are easily

0.77

5.5c
3.2

adsorbed on the electrode surface.113,125 Thus, electro-

chemical water splitting in acidic electrolytes is oen
preferred. However, achieving full water splitting catalysis in
Mass activitya (A

acidic electrolytes is still an urgent task due to the lack of

acid-stable electrocatalysts, especially for the OER. To date,
mgPt1)

only a few noble metals have established a relatively reduced

0.8575

0.095d
0.249

0.504

0.504
0.87b
2.24

overpotential toward the OER and particularly superior

3.5

stabilities under acidic conditions. In line with this, Qiu et al.

Nanoparticles

Nanoparticles

Nanoparticles

designed a nanoporous AuPtPdCuNiAl (np-AuPtPdCuNiAl)

Nanoporous

Nanoporous

Nanoporous

Nanoporous

catalyst, which exhibited excellent HER activity and stability

Structural

Nanotube
feature

in a 0.1 M HClO4 electrolyte with much lower Pt loading

arrays

compared to the commercial Pt/C catalyst. 64 np-AuPtPdCu-

NiAl exhibited an HER mass activity of 6.9 A mgPt1, which
was 5.5 times higher than that of Pt/C (1.3 A mgPt1) at 0.07
VRHE. Moreover, the np-AuPtPdCuNiAl catalyst retained its
compositions

initial HER activity aer 2000 potential cycles, indicating its

Number of

excellent stability. Furthermore, HEA-based electrocatalysts

were used as HER/OER bifunctional electrocatalysts in acidic
electrolytes. Jin et al. reported various nanoporous HEA
5
6

Pt52Ag8Cu12Ni9Co9Fe10 6

5
5

electrocatalysts for the OER and HER in acidic electrolytes

(Fig. 5c–e)63. The authors added several transition metal
PdCuNiCoFe NTAs
np-PtPdCuNiCoAl

PtPdNiCoFe/CNF

Co10Fe11 – 3 min

elements to ternary nanoporous IrNiAl (np-IrNiAl), to form

np-PtCuNiMnAl

Pt50Ag8Cu10Ni11
np-PtIrOsRuCu

np-PtIrOsRuCu
Reaction Catalyst name

quaternary np-IrNiCoAl and quinary np-IrNiCoXAl (X ¼ V, Cr,

Cu, Nb, and Mo) catalysts. The addition of the h element
to np-IrNiCoAl resulted in different effects on the OER
performances. Among the prepared catalysts, np-IrMoNiCoAl
exhibited the highest OER activity in a 0.5 M H2SO4 electro-
Table 2

lyte, whose overpotentials to drive the current densities of 10

MOR
ORR

or 20 mA cm2 were 233 and 255 mV, respectively (Fig. 5d).

a

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Journal of Materials Chemistry A Highlight

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Fig. 5 (a and b) PtAuPdRhRu HEA NPs supported on XC-72 carbon as a HER catalyst. (a) HAADF-STEM image and corresponding EDX elemental
mapping analysis of AuPtPdRhRu HEA NPs/carbon. (b) HER polarization curves of HEA-NPs/carbon in 1.0 M KOH solution. Reproduced with
permission (ref. 70). Copyright 2019, Wiley-VCH. (c–e) Nanoporous IrMoNiCoAl as an OER catalyst. (c) HAADF-STEM image and corresponding
EDX elemental mapping analysis of the nanoporous IrMoNiCoAl catalyst. (d) OER polarization curves of various nanoporous HEA catalysts. (e)
Potential changes of nanoporous HEA catalysts to reach a current density of 60 mA cm2. Reproduced with permission (ref. 63). Copyright 2019,
Wiley-VCH.

Moreover, the durability of quinary np-IrMoNiCoAl sur-
passed that of ternary np-NiCoAl, as indicated by the changes
in the overpotential to drive a current density of 60 mA cm2
aer 7000 potential cycles: 11.5 and 70.3 mV for np-IrMoNi-
CoAl and np-NiCoAl, respectively (Fig. 5e). Aer the dura-
bility test, the ve elements in the np-IrMoNiCoAl catalyst
were uniformly distributed without any visible phase segre-
gation measured by STEM-EDX elemental mapping analysis.
Therefore, this enhanced stability of quinary np-IrMoNiCoAl
might have originated from the suppressed atomic diffusion
during potential cycling due to the high-entropy stabilization
effect based on DGmix ¼ DHmix  TDSmix: TDSmix would
overcome DHmix and dominate the overall DGmix, originating
from higher mixing entropy.126 Moreover, np-IrMoNiCoAl
exhibited high activity toward the HER, whose overpotential
to drive a current density of 10 mA cm2 was 18.5 mV,
demonstrating its bifunctional activity. The authors also
used a two-electrode system for overall water splitting in a 0.5
M H2SO4 electrolyte, and the np-IrMoNiCoAl catalyst
exhibited superior activity and stability to np-IrNiAl and Pt/
C–IrO2 system. The electrocatalytic performances of
nanostructured HEA-based catalysts toward the OER and
HER are summarized in Table 3.
The electrocatalytic application of HEA NPs in the selective
CO2 reduction reaction (CO2RR) has also been reported
recently. For example, Nellaiappan et al. reported quinary fcc-
AuPtAgPdCu NPs as an efficient CO2RR electrocatalyst toward
CH4 and C2H4 in the low overpotential region.65 The ve
elements in the quinary HEA NPs were homogeneously
distributed, whose chemical environments adopt metallic
characteristics determined by XPS analysis except for Cu;
a small amount of Cu2+ content was observed. The quinary fcc-
AuPtAgPdCu NPs obtained superior selectivity toward the
CO2RR in the low overpotential region, that is, FEmethane ¼
38.2% and FEethylene ¼ 29.5% at 0.9 VAg/AgCl (0.3 VRHE) in
a CO2-saturated 0.5 M K2SO4 electrolyte (FE: faradaic efficiency).
Based on their DFT calculation, the excellent electrocatalytic
activity toward the CO2RR has mainly originated from redox-
active Cu content in AuPtAgPdCu, while other elements provide
an additional synergy in the CO2RR. Also, the long-term stability
of the catalyst was veried by a chronoamperometry test for 5 h
in a CO2-saturated 0.5 M K2SO4 electrolyte.

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Highlight Journal of Materials Chemistry A

3.2. Finding the optimum catalyst composition and

@ 0.07 VRHE.
Ref.

63

63
14

69
72
63
64

16

70
structure of HEA-based electrocatalysts
To realize the full potential of HEA-based electrocatalysts, it is

0.5 M H2SO4

0.5 M H2SO4

0.5 M H2SO4
0.5 M H2SO4

0.5 M H2SO4
0.1 M NaOH
1.0 M KOH

0.1 M KOH

1.0 M KOH
1.0 M KOH
Electrolyte
critical to investigate the origin of their activity and stability.
The origin of the catalytic activity of HEA-based electrocatalysts

1
@ 0.07 VRHE. A mgPt+Pd+Au
may arise from the complex interplay between the different
elements within the solid solution. However, it is important to
emphasize that other related factors such as strain effects or
60 mA cm2 aer 7k cycles

interparticle distances may also affect the electrocatalytic

f
100% aer 2k cycles
11.5 mV increased @

activity. The combinatorial screening approach to develop new

90% aer 2k cycles
50 h @ 10 mA cm2

8 h @ 100 mA cm2

8 h @ 100 mA cm2
50 h @ 1.52 VRHEc electrocatalysts with ideal material compositions was not given
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1 h @ 1.6 VRHE

proper attention for a long time. Reddington et al. rst sug-

Durability test

gested this method in 1998 to nd the most active compositions

for electrocatalysts.73 This study illustrated the identication of

1
for the HER. @ 1.5 VRHE. Overall water splitting. @ 1.7 VRHE including carbon black. A mgPt
most active compositions among a 645-member electrode array
—

containing ve elements, through the facile conversion of ions

generated in an electrochemical half-cell reaction into a uo-
e
(mV dec1)
Tafel slope

rescence signal (Fig. 6a). However, it took almost two decades

before a follow-up study was reported. Li et al. applied a high-
55.2

59.8

33.2
46

150

28

41
66
62

throughput electrochemical characterization coupled with

—

a scanning droplet cell (SDC) approach, to guide the design of

a nanostructured, quaternary Pd-based solid solution electro-
Overpotential

catalyst for the ORR in an alkaline medium.127 Similarly, Löffler

et al. set out to investigate the intrinsic electrocatalytic activity
(mV)a

240
Summary of the electrocatalytic OER and HER performance of high-entropy alloy-based catalysts

of NPs towards the ORR in an alkaline medium.77 The strategy

190g
18.5
233

377

107
172
—

was comprised of combinatorial co-sputtering into an ionic

liquid followed by potential-assisted immobilization, which
Mass activity

allowed the precise tuning of the elemental composition of

d
(A mg1)

multicomponent metal alloy NPs. An ultrahigh vacuum depo-

0.104d
0.115b

sition system with a multiple cavity holder and specially

6.9e
2.5f
—

—
—

—
—
—

designed cover was utilized to assist the methodical selection of

element combination and composition (Fig. 6b). This kind of
Structural feature

combinatorial synthesis of HEA NPs by using a SDC cell could

also be coupled with the CTS method, as Yao et al. reported
Nanoparticles
Nanoparticles

Nanoparticles
Nanoporous

Nanoporous
Nanoporous

Nanoporous
Nanoporous

(Fig. 6c and d).75 They synthesized a series of NPs, from ternary

c

(PtPdRh) to octonary (PtIrPdRhRuNiCoFe) composition. Based

Bulk

on their screening by using a SDC cell, the quinary PtPdNiCoFe

composition exhibited the highest ORR activity in an alkaline
electrolyte, which corroborates with the activity tendency
b
compositions

measured by using a conventional rotating disk electrode (RDE)

Number of

set-up.
Meanwhile, recent reports have proposed relevant theoret-
ical models, including the exploitation of computational
5

5
5
5

5
6

2

studies (or rst principles studies) and machine learning-

@ 10 mA cm for the OER; @ 10 mA cm
AuPtPdRhRu NPs/C – 700  C

assisted design studies, which helped identify the active cata-

lytic sites and HEA surfaces. For instance, Batchelor et al. re-
PtLaNiCoFe HEMG-NP

ported that the interaction of multiple adjacent elements within

MoNiCoFeCr-1150
np-AuPtPdNiCuAl

a HEA system is the basis of the huge possible number of

np-MoNiCoFeAl
np-IrMoNiCoAl

np-IrMoNiCoAl

different active sites, which include a wide range of adsorption

Catalyst name

np-IrNiCoVAl

NiCoFeMnCr

energies.128 They developed a model that predicts the adsorp-

tion energies of active sites based on the composition of the
@ 30 mA cm2.

local binding sites of quinary PtIrPdRhRu HEAs. They proposed

2

that altering the HEA surface that contains enough binding

sites with near-perfect adsorption energies may provide
Reaction

a simple means of surpassing the activity of pure Pt. Aer they

Table 3

HER
OER

veried the theoretical stability of the HEA, based on the recent

a
g

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Journal of Materials Chemistry A Highlight

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Fig. 6 (a) Combinatorial screening of PtIrOsRhRu catalysts toward the methanol oxidation reaction. (Top) Pt–Rh–Os ternary array in a 6 M
aqueous methanol (pH 6) quinine indicator. Three photographs show an image under white light, and fluorescence images at low and high
overpotentials, respectively. (Middle) Unfolding of a quaternary phase diagram and mapping into two dimensions. (Bottom left) At a resolution of
10 different compositions along each binary edge, a quaternary map contains 220 unique spots. (Bottom right) Borohydride-reduced, inkjet-
printed array of electrocatalysts on carbon paper. Reproduced with permission (ref. 73). Copyright 1998, AAAS. (b) Strategy for evaluation of the
intrinsic activity of HEA NPs. Reproduced with permission (ref. 77). Copyright 2018, Wiley-VCH. (c and d) Scale-up synthesis and fast screening of
HEA NPs for electrocatalytic reactions. (c) Schematic illustration of the combinatorial and high-throughput synthesis of uniform HEA NPs. (d) The
scanning droplet cell setup and patterned samples on the copper substrate: CE, counter electrode; RE, reference electrode; WE, working
electrode. Reproduced with permission (ref. 75). Copyright 2020, National Academy of Sciences.

criteria to design HEAs, they calculated the adsorption energies
of ORR intermediates, *OH and *O adsorbates, on the HEA
surface. The developed model was able to link the local atomic
environment around the atoms, with which the adsorbate
binds, to the adsorption energy.
Similarly, Löffler et al. emphasized the lack of explanation of
the origin of catalytic activity for HEA NPs; the investigation of
the properties of HEA nanomaterials has started only recently.8
They stressed that the properties of the active sites are mainly
regulated by the electronic interaction of neighbouring atoms.
In particular, the different atom sizes trigger lattice distortions
and strain effects, which subsequently affect the local electronic
properties. Accordingly, the arrangement of all elements next to
each other provides unique active sites consisting of multiple
elements. Therefore, they suggested that the distance between
the active sites and the distance of the neighbouring atoms
from the active sites are critical factors to consider, as they can
dene the catalytic activity and properties of an electrocatalyst.
Moreover, they investigated the inuence of adding or replacing
elements on the shape and activity of catalytic response curves
of HEA NPs toward the ORR, through a theoretical study of the
adsorption energy distribution pattern (AEDP).129 They
performed a qualitative adsorption peak separation within the
AEDP, which is directly correlated with the current wave sepa-
ration. In principle, the number of current waves is equal to the
number of elements in a HEA or complex solid solution system.
The intensities of these waves are affected by the molar ratio of
elements, while the activity is regulated by the relative position
of the peak maximum with respect to the optimal binding
energies (Fig. 7a). The assessment of the intrinsic activity of the
most active current waves is critical to the identication of the
optimum combination of elements for HEA NPs and to the
reduction of the number of catalysts that need to be investi-
gated experimentally. The composition of these HEAs can be
further optimized by investigating the current magnitudes of
the most active wave segments. Fig. 7b illustrates the effect of
adding or replacing elements on the catalytic activity of HEA
NPs.
Furthermore, machine learning (ML) tools can estimate the
relationship between the catalytic descriptors and properties of
HEAs without dealing with enormous simulation cells, which
parametric approaches such as DFT calculations oen deal
with.132 For example, Pedersen et al. aimed to overcome the
limitation of calculation of the available adsorption energies on

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Fig. 7 (a) Simplified scheme to illustrate active site distribution within one adsorption peak. Active sites of similar activity are grouped together
and summarized as one site, whose intensity depends on the amount of similar sites. (b) Schematic illustration of correlations between complex
solid solution (CSS) NP structure, its effect on the adsorption energy distribution pattern, and the respective electrochemical response in the
kinetic region. The shift in the energy of the individual adsorption peaks upon replacement or addition of elements depends on the material-
inherent properties based on the complex interaction with the other elements and only a few arbitrary examples of the many options are
visualized. Reproduced with permission (ref. 129). Copyright 2020, Wiley-VCH.

the catalyst surface for H2 formation and CO reduction, with the
use of a facile surface microstructure model and supervised ML
tools.131 By systematically training the Gaussian process
regression (GPR) model with minimum catalytic descriptors
(only the criteria for CO and H adsorption energies were stored),
they were able to predict the adsorption energies of all possible
catalytically active sites. Using these results, they produced
a model map, which can trace the changes in selectivity and
activity for every ratio of elements in the HEAs. Through these
ML design studies, the locally optimal disordered alloy
compositions for HEAs, GaZnCuNiCo and AuPtAgPdCu were
successfully determined. Likewise, Huang et al. addressed the
issue of design and phase selection in HEAs by applying three
common ML algorithms: (1) K-nearest neighbours (KNN), (2)
support vector machines (SVM), and (3) articial neural network
(ANN).130 They realized that regardless of which ML algorithm is
used, the accuracy of the training process can always be opti-
mized by methodically adjusting the hyperparameters or cata-
lytic descriptors involved. However, the suitability of the model
is highly dependent on the ability of ML tools to separate the
unknown data (testing data). In addition, they found that
among the recent criteria for the design of HEAs, atomic size
difference and valence electron concentration are relevant
parameters to the prediction of the phase selection in HEAs,
based on the results of testing accuracy levels.
4. Outlook and future prospects
The catalytic activity of an electrocatalyst is highly dependent on
the number of exposed active sites and the stability of the
intrinsic activity of active sites. Structural engineering of
nanocatalysts has been extensively explored to increase the
number of exposed catalytically active sites of a catalyst via the
modication of the morphology, enhancement of the specic
surface area, particle size and pore size variation, the
introduction of defects and vacancies, and manipulation of
crystal facets and phases.133–135 Therefore, to take full advantage
of the intrinsic activity of catalytically active sites, extensive
modication of the structure and composition of the present
catalyst is necessary for HEA NPs. The present limitations, low
specic surface area, uncontrolled morphology and exposed
facets, and wide particle size distribution, greatly mitigate the
catalytic activity of HEA-based electrocatalysts.
Among the synthetic strategies for HEA NPs presented in
Section 2, selective dealloying, the CTS method, and combina-
torial approaches have shown particularly promising results in
terms of controlling the atomic concentration within HEA
systems and securing single-phase solid solutions. At the
present time, the dealloying method to fabricate nanoporous
metals from metallic alloys involves multiple step processing
procedures.136 For the fabrication of HEA NPs, a combination of
traditional metallurgy, fast cooling, and selective dealloying is
oen employed, in which the dealloying process of the designed
precursor alloys controls the composition of these HEAs. Al-
based precursor alloys are oen used for selective dealloying, as
these compounds are easily leached out by a strong base or
acid.63,64 In the same context, phase-segregated multi-metallic
nanocrystals could be transformed into solid solution alloy
nanostructures with hollow or porous structures. In other
words, the transformation process of well-dened NPs to form
a hollow nanostructure via chemical etching with acids is very
similar to the process of chemical dealloying for nanoporous
HEA fabrication. Therefore, it is possible that well-dened HEA
nanostructures could be successfully synthesized from pre-
synthesized, multi-metallic nanostructures. For example, Park
et al. reported the fabrication of ternary IrCuNi alloy nanoframe
structures from phase segregated ternary IrCuNi nanocrystals
by HCl treatment.137 Although three contents in the initial
nanocrystal are separated, the resulting IrCuNi ternary

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Journal of Materials Chemistry A
nanoframe exhibited a solid solution alloy. Similarly, Saleem
et al. reported a quaternary, PtAgPdRh solid solution alloy
nanoframe structure from phase-segregated PtAgPdRh octahe-
dral nanoparticles via KI and base treatment.138 Also, the
fabrication of porous-quaternary solid solution nanocrystals
from well-dened quaternary nanocrystals was reported with
BiPtCuMn139 and BiPtAgCo140 compositions, and this strategy
could be extended to quinary or more complex HEA
compositions.
Thus far, critical assessment of the conditions applied
during dealloying, such as the concentration and kind of acid or
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base, temperature, and dealloying time, has been overlooked,
although parameter optimization is vital to the precise control
of the particle size and atomic concentration of HEAs. The
importance of acid treatment conditions in a binary system is
extensively studied by many researchers. For example, binary
PtNi rhombic dodecahedral nanocrystals could be transformed
into hollow PtNi rhombic dodecahedral nanoframes via acid
treatment. When acetic acid is used, the nal PtNi nanoframes
adopt Pt64Ni36 composition, whereas a similar process with
HNO3 resulted in Pt75Ni25 composition, as Chen et al. re-
ported.141 Also, the relative ratio of Pt and Ni in the PtNi
nanoframe affected the electrocatalytic ORR activity and dura-
bility because the roughness of the catalyst surface was differed
by their composition. Therefore, the dealloying process to
fabricate HEA nanostructures should be considered more
carefully to precisely control their composition. In addition, the
synthetic strategies of HEA-based electrocatalysts could be
further honed by considering the energetics in the local atomic
structure of HEA NPs. For example, grain boundaries, atomic
vacancies or hetero-interfaces in nanocrystals could serve as
effective channels of atom diffusion.142,143 Therefore, to impede
the phase segregation and maintain the single-phase solid
solution HEA NPs, these structural features might have to be
eliminated post-synthetically. Inversely, phase-segregated
multicomponent nanocrystals could be transformed into single
solid-solution HEA NPs by facilitating the diffusion of atoms.
Furthermore, it is imperative to develop in-depth analysis
skills to characterize the overall structure of HEA NPs. Trans-
mission electron microscopy (TEM), high-resolution STEM (HR-
STEM), EDX, and electron energy loss spectroscopy (EELS) at
the subnanometre scale are powerful characterization tools to
assist the evaluation of active catalytic sites.66,144–146 The
combination of these techniques can show the subsurface
layers of HEA NPs, which can reveal some of the activity-related
effects, such as the strain effect between the multicomponent
neighbouring atoms in the nanoscale structure and the distri-
bution of elements on specic surface facets. Likewise, XPS and
X-ray absorption ne structure (XAFS) spectroscopy are efficient
tools to determine the local atomic structure and overall elec-
tronic structure of HEA-based electrocatalysts. These high-
resolution characterization techniques are crucial to the
establishment of the relationship between the structure and
activity of high-entropy alloys.
In addition to developing synthetic strategies to HEA NPs
and analysis skills for HEA NPs, computational studies and ML-
assisted design studies should also be developed to predict the
14858 | J. Mater. Chem. A, 2020, 8, 14844–14862
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Highlight
nanostructure and composition of alloys that have not been
fabricated. The predicted structure and property relationships
might aid the preparation of new HEA NPs with targeted
performances.147,148 To screen out the vast number of possible
combinations from calculation studies, assigning the following
factors as priorities may have a signicant impact if the goal is
to optimize the structural arrangement of atoms in HEAs: (1)
most promising ratio of the elements, which can be correlated
with the composition of actual HEAs and can be investigated
experimentally aerward, and (2) position of every atom within
the system, including the distance of an atom from the centre of
active sites and from neighbouring atoms.8 Subsequently, the
selected combination of elements from the screened results
might be submitted to machine learning-assisted design
studies. The results from these studies can then be used in
actual experiment procedures to obtain the desired design of
HEA NPs, which represents a time-saving and cost-effective
approach to nd the optimum composition and surface struc-
ture of HEA-based electrocatalysts.
At the present time, although the electrocatalytic activity of
HEA-based electrocatalysts is still inferior to that of record-high,
surface-engineered noble-metal based electrocatalysts, such as
PtNi jagged nanowires for the ORR under acidic conditions
(13.6 A mgPt1),149 certain HEA-based electrocatalysts can
surpass the benchmark electrocatalysts such as Pt/C and Ir/C
for various electrocatalytic reactions. Moreover, the notable
catalytic activity and durability of several single-phase solid
solution HEA NPs point to the great prospect of this particular
material class as electrocatalysts; the notable catalytic activity of
HEA electrocatalysts towards water splitting application has
been attributed to the decreased energy barriers during elec-
trocatalysis,28 and excellent durability, which can maintain high
capacity retention even aer 100 000 continuous cycles,64 has
been linked to the excellent corrosion resistance of the material
and the ability to limit the diffusion of atoms. Moreover, elec-
trocatalytic reactions such as the ORR, OER and CO2RR are
accompanied by multi-electron and multi-proton transfer, and
therefore there are fundamental issues for the performance
enhancement of the catalysts, which is limited by the scaling
relationship.150 In this context, the surface of solid-solution
HEAs with multifunctionality might produce an alternative
pathway of the reaction, which can overcome the limitation on
the scaling relationship.8 Hence, the following research points
would be relevant for future studies.
 In-depth interpretation of activity curves and Tafel slopes
to evaluate the catalytic properties of HEA NPs.
 Evaluating the strength of stability of new nanoscale HEAs,
especially under harsh electrocatalytic conditions.
 Understanding the effect or inuence of oxide formation
on the surface of HEAs at high anodic potentials.
 Development of advanced synthetic methods that can
improve the morphology, electrochemically active surface area,
and pore size distribution of HEA NPs.
 Modication of the composition and surface structure of
HEA-based electrocatalysts by precise calculation of the
adsorption energies of catalytically active sites and
This journal is © The Royal Society of Chemistry 2020

Highlight
consideration of the distance between the active site centres
and neighbouring atoms.
 Exploiting sub-nanometre characterization tools to assist
the evaluation of active catalytic sites.
In summary, enormous effort is still needed to further
improve the general electrocatalytic performance of HEA NPs,
but it should be emphasized that the potential of these mate-
rials as efficient electrocatalysts is irrefutable. This report hopes
to highlight new research avenues and to provide stimulating
ideas on how to further modify the structure of high entropy
alloy nanoparticles for optimal catalytic performances.
Published on 06 July 2020. Downloaded by Korea University on 8/6/2020 2:09:06 AM.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
This work was supported by the National Research Foundation
of Korea (NRF) funded by the Ministry of Science and ICT (NRF-
2020R1A2B5B03002475, NRF-2019M3E6A1064709 and
NRF2019R1A6A1A11044070), Korea Basic Institute under the
R&D program (Project No. C38530) supervised by the Ministry of
Science, and Korea University Future Research Grant (KU-FRG).
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