High-Entropy Materials For Catalysis

SCIENCE ADVANCES | REVIEW
MATERIALS SCIENCE Copyright © 2021

The Authors, some
High-entropy materials for catalysis: A new frontier rights reserved;
exclusive licensee
American Association
Yifan Sun1 and Sheng Dai1,2* for the Advancement
of Science. No claim to
Entropy plays a pivotal role in catalysis, and extensive research efforts have been directed to understanding the original U.S. Government
enthalpy-entropy relationship that defines the reaction pathways of molecular species. On the other side, surface Works. Distributed
of the catalysts, entropic effects have been rarely investigated because of the difficulty in deciphering the under a Creative
increased complexities in multicomponent systems. Recent advances in high-entropy materials (HEMs) have trig- Commons Attribution
gered broad interests in exploring entropy-stabilized systems for catalysis, where the enhanced configurational NonCommercial
entropy affords a virtually unlimited scope for tailoring the structures and properties of HEMs. In this review, we License 4.0 (CC BY-NC).
summarize recent progress in the discovery and design of HEMs for catalysis. The correlation between composi-
tional and structural engineering and optimization of the catalytic behaviors is highlighted for high-entropy alloys,
oxides, and beyond. Tuning composition and configuration of HEMs introduces untapped opportunities for ac-
cessing better catalysts and resolving issues that are considered challenging in conventional, simple systems.
Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

INTRODUCTION range of the catalytic active sites. In addition, pronounced lattice
Entropy-driven behaviors of molecular species, including adsorp- distortion in HEMs lowers the overall system energy and thus facil-
tion of reactants, as well as translation, rotation, and vibration of itates activation and transport of active species. For example, favor-
intermediates bound to active sites, fundamentally determine the able formation of oxygen defects in entropy-stabilized oxides has
reaction pathway of catalytic reactions and have thus been exten- shown to improve the catalytic performances for various oxidation
sively studied (1). For instance, entropic contributions are impor reactions (8, 9). Modifying the entropic effects also constitutes a
tant driving forces that accelerate enzyme catalysis by lowering the transformative paradigm, making it possible to mitigate and fun-
activation energy (2). For acid catalysis in zeolites, enthalpy-entropy damentally resolve some of the challenging issues in traditional,
compensation is mediated by the molecular confinement in micro- enthalpy-dominated systems.
pores (3). Beyond catalysis, separation of structural isomers can be Several recent papers have reviewed the catalytic applications
realized through preferential adsorption of the targeted molecules mainly based on high-entropy alloys (HEAs), while entropy-stabilized
in carefully designed zeolite cages, which is dependent on the rota- systems beyond HEAs have been rarely covered (10–16). Elucida-
tional entropy correlated with the internal space of the pores (4). tion of the structure-property relationships of HEMs, particularly
Exquisite tuning of the enthalpic and entropic parameters gives rise across different subcategories, is crucial to leverage the enhanced
to efficient optimization of stabilization and transformation of mol- entropic effects for catalysis. Rapid development of HEMs also
ecules under various conditions. necessitates thorough comparisons to unveil the enthalpy-entropy
Entropy-centered discussions on the catalyst side, especially the correlation on the catalyst side. Here, we summarize recent advances
configurational entropy dictated by the mixing of different compo- in HEMs for catalysis. We first introduce the evolvement from con-
nents, have not remained in balance. Most studies have focused on ventional multicomponent systems to entropy-stabilized solid solu-
topics that can be rationalized using enthalpic parameters, such as tions from a fundamental perspective. Advanced synthetic and
metal-support interactions depending on the relative strengths of characterization techniques coupled with powerful computational
the metal-metal and metal/oxide bonds (5), and charge transfer– tools provide atomistic insights into the surface, interface, lattice,
induced stabilization of transition metal oxide nanoparticles on lay- and defects of HEMs, which are important to understand the asso-
ered perovskite oxides (6). Meanwhile, entropic factors have been ciated catalytic behaviors. Case studies of HEAs, high-entropy
underexplored because of the limited configurational tunability in oxides (HEOs), and novel high-entropy systems for catalysis are then
multicomponent systems, and increased structural and composi- performed, highlighting the link between modulation of the geo-
tional complexities that are difficult to decouple. Entropy-directed metric and electronic properties and optimization of the catalytic
strategies have been used to fabricate well-tailored nanocrystal as- properties. In the end, we discuss the upcoming opportunities and
semblies (7), whereas their applications in catalysis are hindered by challenges for this emerging and highly promising field. We hope
the compromised stabilities under reaction conditions. the insights provided here can help probe the origin for the traits of
Recent progress in high-entropy materials (HEMs) has afforded a HEMs, which present a game-changing forefront for the discovery
versatile platform to investigate the influence of entropy on the catalyst and design of high-performance, cost-effective catalytic materials.
side. A broad scope of entropy-stabilized multicomponent systems
with tailored compositions, structures, and architectures can be
readily accessed using unconventional synthetic methods. Confining FROM MULTICOMPONENT SYSTEMS TO HEMs
multiple atomic species into the same lattice, which is enabled by Alloying is one of the most common and effective approaches to
the enhanced entropic contributions, drastically expands the tuning constructing multicomponent systems with tunable properties, where
different atoms are randomly distributed or packed in an ordered
1 manner for intermetallics. Unique yet advantageous catalytic prop-
Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831,
USA. 2Department of Chemistry, The University of Tennessee, Knoxville, TN 37996, USA. erties emerge in alloys due to the pronounced multielemental inter-
*Corresponding author. Email: dais@ornl.gov actions. This has been evidenced in numerous cases, such as lattice
Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 1 of 23

oxygen activation in the CeO2-ZrO2 solid solutions (17) and im- ability to confine multiple principal elements in a single lattice is
proved electrochemical activation of CO2 through altering the intriguing for the design of advanced catalysts with desirable ac-
atomic ordering of the AuCu nanoparticles (18). For cases where tivity, selectivity, and stability. First, properties of traditional
individual species are not miscible to each other, phase segregation alloys are mainly determined by one or two principal elements. In-
unavoidably constrains the tunability in composition and structure. corporating dopants in low concentrations would only fine-tune
Delicate control is also needed to construct active interfacial do- the predefined features. Discovery of HEMs makes it possible to
mains, as impurity formation could block the active sites from sur- embrace unprecedented compositional diversities and structural
face exposure. Therefore, maintaining the single-phase state is vital complexities. In parallel, the multielemental incompatibility that
to realize atomic mixing of different species and obtain synergistic originated from the large enthalpic differences can be compensated
properties that are inaccessible with each individual constituent. by the enlarged configurational entropy. The concentrations of the
From a fundamental perspective, formation of a uniform single- principal elements can be elevated in this way, which may even sur-
phase or a multiphase state is dependent on parameters including pass the miscibility barriers in the bulk phase (25). Accordingly, a
electronegativity difference, valence electron concentration, atomic broader range of geometric and electronic properties become acces-
size difference, and mixing entropy and mixing enthalpy (19). The sible. Second, severe lattice distortion caused by the atomic size dif-
first three factors are intrinsic properties and thus difficult to alter, ference induces a thermodynamically nonequilibrium state (10). This
whereas enthalpic and entropic contributions during the mix of dif- could hypothetically reduce the energy barrier for adsorption, acti-
ferent components can be manipulated with external approaches. vation, and conversion of molecules. Distortion-derived local strain,

In general, the phase stability in a multicomponent system can be which is inevitable for a diverse and complex system like HEM, also
estimated using the Gibbs free energy equation has substantial impacts on modifying the energy levels of bound in-
termediates (26). Third, the higher diffusion activation energies of
 G mix =  H mix  − T S mix
HEMs result in sluggish diffusion kinetics, which has been recog-
nized as the main impetus for the enhanced chemical, thermal, and
where Gmix, Hmix, and Smix are the changes of the Gibbs free mechanical stabilities (27). Counterintuitively, the entropy-stabilized
energy, mixing enthalpy, and mixing entropy, respectively, and T is single-phase state would be more thermodynamically favorable at
the thermodynamic temperature (20). In this way, the Gmix value even higher temperatures according to the Gibbs free energy equation,
is directly determined by the relative values of Hmix and −TSmix. while how to maintain the exposed active sites on an antisintering
A negative value for Gmix indicates that the system is favorable surface becomes challenging. These unconventional yet advanta-
toward a single-phase state with random distributions, while a pos- geous traits render HEMs as attractive candidates for better cata-
itive one suggests a thermodynamic-driven phase separation. The lysts, as well as versatile platforms to probe the enthalpy-entropy
mixing entropy in an ideal case can be expressed as below correlations on the catalyst side.

 S mix = − RΣ x  i ln x  i
SYNTHESIS AND CHARACTERIZATION OF HEMs FOR CATALYSIS
where R is the gas constant and xi is the mole fraction of the ith At sufficiently high temperatures, the entropic contributions sur-
component (20). It can be deduced that equal molar fractions of pass the enthalpic ones, leading to a homogeneous yet random dis-
each component would maximize the value for Smix, which are cal- tribution of different elemental species in the same lattice (28).
culated to be 1.10R, 1.39R, 1.61R, 1.79R, and 2.20R for equiatomic However, the low surface area brought by the high-temperature
ternary, quaternary, quinary, senary, and nonary alloys, respectively operation drastically limits the utilization of HEMs for catalysis.
(20, 21). The value of Hmix, on the other hand, varies in phase- Accessing nanostructures with increased surface area and more ac-
segregated mixtures and ordered intermetallics, leading to different tive sites has thereby motived the exploratory synthesis of HEMs,
critical temperatures at which the entropic contributions (TSmix) which can be broadly classified into three main categories. The first
exceed the enthalpic ones (Hmix) (22). For single-phase solid solu- one is to rely on the nonequilibrium process, such as the carbother-
tions, the Hmix value is generally considered negligible, which is mal shock technique and the fast moving bed pyrolysis (FMBP)
the same for the nonconfigurational entropy (23). Therefore, the technique (29, 30). The thermodynamically favorable high-entropy
above two equations qualitatively depict the enthalpy-entropy cor- phases are kinetically trapped during the ultrafast heating-cooling
relations at different temperatures, and two key conclusions can be process. The short growth time in the scale of seconds or less also
drawn: Configurational entropy will become the determining factor ensures formation of nanosized particles with enlarged surface
for the phase stability of the multicomponent system at sufficiently areas. The second one is to exploit the techniques that create local
high temperatures, and incorporating more species with near-equal extreme environments, such as ball milling and solvothermal syn-
mole fractions markedly increases the entropic contributions, which thesis (31, 32), to realize atomic mixing of different species. It is
subsequently lowers the overall free energy. These two inferences, worth mentioning that the overall operation conditions of these
which correlate the adjustment in composition and configuration methods still remain mild and thus benefit scale-up implementa-
with phase stability in multicomponent systems, lay basic founda- tions. The third category is to turn to external factors in the liquid
tions for understanding the formation and properties of HEMs. phase, such as solvent and ligand molecules in colloidal and polyol
In 2004, two groups independently reported a new type of alloys solutions (33, 34), to facilitate formation of nanoscale HEMs at rel-
(21, 24), where multiple (≥5) principal elements are unexpectedly atively low temperatures (~200° to 300°C). The surface capping
stabilized in a homogeneous single-phase state. These two discoveries ligands can modify the energetic barrier for homogeneous nucle-
are considered the prototype of HEAs, and the concept of entropy- ation and growth, yielding high-entropy nanocrystals instead of phase-
induced stabilization has therefore been gradually established. The segregated heterostructures.

Choosing catalytic reactions for HEMs is closely related with temperature-dependent evolution of local disorders in Al1.3CoCrCuFeNi
their microstructure and surface properties, which vary according using neutron PDF and demonstrated the great potential of com-
to different synthetic approaches. For example, freestanding colloidal plex systems beyond single-phase solid solutions.
and polyol HEMs with good solution dispersibilities can be readily Electron microscopy techniques, mostly including scanning elec-
used for liquid-phase batch conversions such as selective hydroge- tron microscopy (SEM), transmission electron microscopy (TEM),
nation and hydrodeoxygenation reactions (35, 36), while supported and scanning transmission electron microscopy (STEM), are depen-
HEMs prepared with the carbothermal shock technique work better dent on the interactions between electrons and specimen and have
for gas-phase reactions such as methane combustion (37). It is also been extensively applied to gain local information such as morphology
viable to combine two or more approaches or modify the existing and size of the materials. SEM covers a larger area of the sample,
protocol to tackle synthetic challenges for obtaining different types whereas TEM is typically more focused on a smaller area with higher
of HEMs. For instance, the hydrothermal method combined with resolutions. STEM, on the other hand, is more versatile with ex-
ball milling produces high-entropy perovskite fluorides (HEPFs) panded functionalities. Annular dark-field STEM (ADF-STEM)
(38), which cannot be successfully prepared using solely hydrothermal- permits atomically resolved visualization of the high-entropy struc-
or mechanochemistry-based methods. Carbothermal shock tech- tures, which unambiguously pinpoints the positions of the different
nique, which was originally developed to prepare HEA nanoparticles, atoms (Fig. 1E). Electron tomography allows three-dimensional
has been successfully extended to the fabrication of HEO and sul- reconstruction based on a series of single-tilted two-dimensional
fide nanoparticles (37, 39). STEM images, yielding a complete picture of morphology and struc-

Despite variation of the synthetic routes to fabricating different ture of nanoscale objects (44). Besides local structures, STEM cou-
subgroups of HEMs, which will be discussed in detail in the follow- pled with energy-dispersive x-ray spectroscopy (EDS) or electron
ing sections, the associated characterization techniques are general- energy-loss spectroscopy (EELS) element maps could clarify local
izable. Ideally, configurational entropy is maximized in a single chemical compositions, which are important to appraise the structure
phase where different constituent atoms are randomly distributed. homogeneity of HEMs. A recent study from Ding et al. (45) eluci-
However, the definition of HEM is flexible and inclusive. As shown dated elemental distribution of the CrMnFeCoNi and CrFeCoNiPd
in Fig. 1A, several possibilities with different degrees of order and alloys using atomic-resolution chemical mapping, providing direct
disorder exist between the phase-segregated heterostructures and experimental evidence for structure and composition tuning of HEAs.
the ideal entropy-stabilized solid solutions. More and more studies STEM-EDS element maps are more frequently applied to HEMs be-
have indicated that local clustering, surface reconstruction, and for- cause of the higher sensitivities to metal elements with higher atomic
mation of interface and vacancy in the multiphase state also bring numbers (46). In comparison, EELS is capable of identifying the
appealing attributes, further necessitating the elucidation of local oxidation states of the target element, yet more sensitive to detect
structures. Topics including identification and quantification of ac- light elements like C, N, and O. Recent progress in environmental
tive sites, mechanistic studies, and optimization of the catalytic per- transmission electron microscopy has fueled burgeoning interests
formances all rely on precise characterization of HEMs, which is in performing operando measurements, monitoring the change of
challenging because of the increased compositional and structural structural and energetic features of catalysts under reaction condi-
complexities. Nanostructuring, which has been widely applied to tions (47).
increase the number of active sites, further complicates the scenario Complementary to EDS and EELS that focus on a small area of
because of the size and facet dependence of the structural parame- the sample, bulk spectroscopic techniques probe the bulk and
ters (11). Despite these challenges, advances have been accomplished surface structures together with the corresponding chemical states.
to use diverse techniques to characterize nanostructured HEMs. X-ray absorption spectroscopy (XAS) is an element-specific tool to
We herein outline the diffraction, microscopic, and spectroscopic study the electronic and geometric parameters of the chemical species.
approaches that have been routinely used (Fig. 1B). X-ray absorption near-edge structure (XANES) allows identification
Diffraction is one of the most readily accessible and well-developed of the oxidation state of the element. Local structure information is
bulk techniques to examine the structures of crystalline materials. attainable by analyzing the extended x-ray absorption fine structure
Powder x-ray diffraction (XRD) patterns enable quick evaluation of (EXAFS) spectra, which presents direct evidence for comparing the
the phase purity in multicomponent system. Several structural pa- chemical environment of different atoms in HEMs (Fig. 1F). Iden-
rameters including lattice parameter, crystallinity, grain size, pre- tifying the catalytic active sites in HEMs can also be realized by
ferred orientation, and strain can be calculated through refinement monitoring the change of the oxidation states of different elements
of the diffraction data. However, limitations exist for the common with operando XAS measurements (48). On the other hand, x-ray
in-laboratory diffraction instruments. Small grain sizes of nanoscale photoelectron spectroscopy (XPS) analyzes the chemical environ-
domains cause severe broadening of the diffraction peaks, which ment including elemental composition and oxidation states on the
makes it difficult to identify the potential impurity peaks (40). Uti- surface and subsurface regions. With etching or sputtering, XPS
lization of synchrotron- or neutron-based diffraction techniques depth profiling probes the chemical compositions at different depths
with high-intensity light sources can mitigate this drawback, afford- starting from the outmost surface. Overlap of the characteristic peaks
ing atomic-level information regarding structure distortion, atom from different elements may complicate interpretation of the core-
displacement, site order and disorder, defect formation, and lattice level XPS spectra, while the associated satellite and plasmonic peaks
strain (41). Meanwhile, total scattering measurements coupled with can be used as informative fingerprints. Auger electron spectrosco-
pair-distribution function (PDF) analysis permits analysis of the lo- py, which is based on a two-hole final state and thus is not affected
cal atomic structures of nanoscale and even amorphous samples by switching excitation lasers or applying various charging correc-
that do not exhibit well-defined Bragg diffraction peaks (42). As tion standards when plotted against kinetic energy, also brings valu-
shown in Fig. 1 (C and D), Santodonato et al. (43) investigated the able information on the chemical state of the target element (49).


Fig. 1. Characterization of HEMs. (A) Schematic showing structures with different degrees of order and disorder between interface formation and ideal random solid
solutions containing five (or more than five) principal elements. (B) Schematic summarizing the diffraction, microscopy, and spectroscopy techniques for the characteri-
zation of HEMs. AES, Auger electron spectroscopy; LEIS, low-energy ion scattering spectroscopy; ETEM, environmental transmission electron microscopy. (C) Room tem-
perature neutron PDF data of the Al1.3CoCrCuFeNi HEA and the simulated pattern based on the cubic structure. (D) Neutron PDF data of the Al1.3CoCrCuFeNi HEA at
1400°C and the simulated pattern based on the local structure model with short-range order. (C) and (D) are reproduced with permission from the Nature Publishing
Group (43). (E) Atomic-resolution high-angle annular dark-field (HAADF) image of the CrMnFeCoNi HEA and corresponding EDS element maps for Cr, Mn, Fe, Co, and Ni.
Reproduced with permission from the Nature Publishing Group (45). (F) Normalized EXAFS spectra of the MgNiCuCoZnOx HEO. Reproduced with permission from the
Nature Publishing Group (http://creativecommons.org/licenses/by/4.0/) (113).
In addition to experimental techniques, various computational screenings of possible structures and compositions in HEMs. The
approaches have been applied to predict and interpret the catalytic obtained results also afford synthetic guidelines for the targeted
behaviors of HEMs. Density functional theory (DFT) calculations high-entropy phase, substantially accelerating the process of mate-
are able to evaluate geometric, electronic, and energetic parameters rials discovery and design. To assess the synthesizability and stability
of the high-entropy catalysts for mechanistic studies (50). Machine of the high-entropy catalysts, molecular dynamics and Monte Carlo
learning emerges as a revolutionary tool to realize high-throughput methods have been used to predict formation and transformation

of HEMs under different conditions (51). These computational tools Notably, HEA nanoparticles composed of up to eight arbitrary
can yield results that are complementary to the experimental data metallic elements (PtPdCoNiFeCuAuSn) were successfully prepared
and even guide the experimental progress. (Fig. 2C). As a proof-of-concept demonstration, the authors ap-
Given the multidimensional complexity in HEMs, it is pivotal to plied the quinary HEA nanoparticles (PtPdRhRuCe) for selective
combine different techniques to draw a complete picture of the sur- ammonia oxidation. The HEA nanocatalysts exhibited excellent
face and bulk characteristics. For example, the average size of the activity (~100% conversion at 700°C), selectivity (>99% selectivity
HEA nanoparticles measured using TEM and STEM can be corrob- toward NO + NO2 rather than N2 + N2O), and stability (no degra-
orated by the grain size estimated with Scherrer analysis of the powder dation over ~30 hours at 700°C), which exceed the performance of
XRD data (52). Oxidation states of the metal species can be deter- the heterostructured PtPdRhRuCe catalysts prepared using the
mined by both STEM-EELS and XANES spectra, and the associated conventional wet impregnation method.
electronic and energetic characteristics can be further analyzed us- Carbothermal shock synthesis of HEA nanoparticles manifests
ing DFT calculations. In addition, understanding the capability and the accessibility of single-phase HEA nanoparticles with intriguing
limitation of each technique is crucial. To assess the structure ho- catalytic properties. The following synthetic work extended to a
mogeneity of HEMs, XRD only works for crystalline materials ex- portfolio of nanoscale HEA architectures ranging from aerosols to
hibiting well-defined diffraction peaks, while STEM-EDS elemental hollow nanoparticles (61–63). However, fabrication of multielemental
mapping can be applied for both crystalline and amorphous sys- alloy (MEA) nanoparticles remains unpredictable because of the
tems. Low-energy ion scattering spectroscopy has a higher surface innumerable elemental combinations. The trial-and-error–type ex-

sensitivity compared with that of XPS but cannot discriminate the periments, which have been long established, are time- and human
different oxidation states (53). For computational investigations, resource–consuming. Hu and colleagues (64) further expedited this
DFT calculations generally yield relatively accurate results based on process by combining computational prescreening with experimental
well-defined local structures. In contrast, molecular dynamics are verification. The authors first applied DFT calculations to predict
more efficient and less expensive since a large number of atoms can the thermodynamic formation barriers of the potential single MEA
be simultaneously computed, while the associated accuracy can be phase, based on which the dynamic movements of the metal atoms at
compromised. synthetic (1500 K) and quenched (298 K) temperatures were further
simulated using a hybrid Monte Carlo and molecular dynamic approach.
Predicted as energetically stable and kinetically favorable using this com-
HEAs FOR CATALYSIS bination strategy, single-phase Ru-4 MEA (Ru0.44Rh0.30Co0.12Ni0.14)
As the prototype of HEMs, HEAs exhibit compelling mechanical and Ru-5 MEA (Ru0.25Rh0.25Co0.2Ni0.2Ir0.1) were prepared by the car-
properties for structural applications, such as outstanding fracture bothermal shock technique. The MEA nanoparticles were applied to
resistance, ultrahigh ductility and strength, and desirable thermal catalyze ammonia decomposition, which is a promising route for
and physiochemical stabilities (54–58). However, bulk HEAs can hydrogen storage because of the high hydrogen densities, conve-
hardly be used for catalytic applications owing to the low surface nience of liquifying with mild pressurization, and better safety (65).
area and limited elemental tunability (59, 60). In this section, we As shown in Fig. 2D, Ru-4 MEA exhibited a higher activity com-
summarize recent advances in fabricating nanostructured HEAs for pared with that of the Ru and RhCoNi samples, and single-phase
gas-phase thermocatalysis and liquid-phase electrocatalysis (Table 1). Ru-5 MEA nanoparticles outperformed the phase-separated sample
Both experimental and computational efforts have been directed to with the same elemental composition. The catalytic performances
understanding the enhanced synergistic effects of the HEA cata- of the MEA nanoparticles are also superior to that of the previously
lysts, where simultaneous incorporation of multiple metal species reported Ru-based catalysts (Fig. 2E), highlighting the competitive-
optimizes surface adsorption properties for catalytic conversions. ness of the composition-tunable MEA nanoparticles.
The Co-Mo binary system with mixed Co-Mo sites is considered
HEAs for thermocatalysis as one of the most promising earth-abundant and inexpensive cata-
Single-phase HEA nanoparticles having enriched catalytic active lysts for ammonia decomposition (66). However, the large miscibility
sites are appealing for catalysis but have remained synthetically gap between Co and Mo prevents continuous tuning of the surface
challenging. Homogeneous mixing of different elements requires properties that span a wide range. Wang and co-workers (67) over-
higher operating temperatures to overcome the thermodynamic came this miscibility issue by leveraging the entropy-induced stabi-
barrier. However, it is difficult to maintain the nanoscale morphol- lization in HEAs. With the carbothermal shock technique, the authors
ogy at elevated temperatures because of migration and aggregation fabricated a series of single-phase CoxMoyFe10Ni10Cu10 (x + y = 70)
of nanoparticles. Hu and co-workers (29) circumvented this dilemma nanoparticles with readily tunable Co/Mo ratios (denoted as HEA-
by developing the carbothermal shock method to synthesize a li- CoxMoy). Compared with bimetallic CoxMoy that tend to generate
brary of composition-tunable HEA nanoparticles. As illustrated in phase-separated Co- or Mo-rich phases, incorporation of Fe, Ni,
Fig. 2A, ultrafast joule heating via electrical current triggers instant and Cu effectively enlarges the entropic contribution, producing a
decomposition of the metal precursors dispersed onto the carbon single solid-solution phase with the face-centered cubic (fcc) structure.
nanofiber support, which facilitates atomic mixing of different met- The HEA-CoxMoy nanoparticles exhibited composition-dependent
als in a liquid-like state. The following rapid quenching process activities for ammonia decomposition. The most active HEA-
enables kinetic control over the thermodynamic mixing regimes. Co25Mo45 catalyst reached a mass-specific rate of 0.74 gNH3 m−2 hour−1 at
As a result, the metal atoms are kinetically trapped in the as-formed 500°C, representing improvement factors of ~24 versus bimetallic Co-Mo
crystalline lattice. This ultrafast heating-cooling strategy surpasses and ~19 versus Ru, respectively. This catalyst also exhibited outstand-
the thermodynamic barrier, producing atomically mixed HEA nano ing thermal and chemical stabilities, showing negligible activity
particles rather than phase-separated heterostructures (Fig. 2B). degradation over 50 hours under the continuous operation at 500°C.

Table 1. Summary of HEAs for thermocatalysis and electrocatalysis. AO, alcohol oxidation; T, thermocatalysis; E, electrocatalysis.
Material Structure Synthetic method Catalytic reaction Ref.
PtPdRhRuCe fcc Carbothermal shock NH3 oxidation (T) (29)
RuRhCoNi and RuRhCoNiIr fcc Carbothermal shock NH3 decomposition (T) (64)
CoMoFeNiCu fcc Carbothermal shock NH3 decomposition (T) (67)
fcc DFT + machine learning ORR (E) (73)
IrPdPtRhRu (calculation)
fcc DFT + machine learning ORR (E) (74)
PtPdRhNi and PtPdFeCoNi fcc Carbothermal shock ORR (E) (75)
AgIrPdPtRu fcc Sputtering ORR (E) (76)
Colloidal synthesis +
PdCuPtNiCo fcc ORR (E) (77)
annealing
AlCuNiPtMn fcc Dealloying ORR (E) (78)

CO oxidation (T), ORR (E),
AlNiCuPtPdAu fcc Dealloying (79)
HER (E), and AO (E)
Amorphous Sputtering ORR (E) (80)
fcc, bcc, and amorphous Sputtering ORR (E) (81)
CrMnFeCoNi
fcc (binary) Laser ablation ORR (E) (82)
Amorphous Sputtering ORR (E) (83)
MnFeCoNiCu fcc Solvothermal OER (E) (84)
FeNiMnCrCu and FeCoNiCrAl fcc + bcc (binary) Arc melting OER (E) (85)
CoCrFeMnNi fcc Laser ablation OER (E) (86)
FeCoNiCrNb Laves phase Dealloying OER (E) (89)
AlNiCoIrMo fcc Dealloying OER (E) (90)
fcc + spinel (binary) Dealloying OER (E) (91)
AlNiCoFeX (X = Mo, Nb, and Cr)
fcc + spinel (binary) Dealloying ORR (E) and OER (E) (94)
AlPdNiCuMo fcc Dealloying AO (E) (92)
RuIrCeNi and RuIrCeNiWCuCrCo fcc Carbothermal shock ORR (E) and OER (E) (93)
FeCoPdIrPt fcc Fast moving bed pyrolysis HER (E) (30)
Ultrasonication-assisted wet
PtAuPdRhRu fcc HER (E) (95)
chemistry + annealing
IrPdPtRhRu fcc Polyol method HER (E) (97)
FeCoNiAlTi L12-type intermetallics Dealloying HER (E) (98)
CuAlNiMoFe fcc + bcc (binary) Dealloying HER (E) (99)
CoFeLaNiPt Amorphous Electrodeposition OER (E) and HER (E) (100)
CoCuGaNiZn and AgAuCuPdPt CO2 reduction (E) and CO
fcc DFT + machine learning (102)
(calculation) reduction (E)
AuAgPtPdCu fcc Melting-cryogrinding CO2 reduction (E) (103)
IrOsPdPtRhRu fcc Polyol method AO (E) (34)
AO (E) and formic acid
AuPdPt fcc Sparking mashup (105)
oxidation (E)
PtNiFeCoCu fcc Colloidal synthesis HER (E) and AO (E) (106)
PdFeCoNiCu bcc Colloidal synthesis HER (E) (107)
RuFeCoNiCu hcp Colloidal synthesis Nitrogen reduction (E) (108)
AO (E) and formic acid
CuAgAuPtPd fcc Melting-cryogrinding (109)
oxidation (E)
fcc Sputtering AO (E) (110)
PtFeCoNiCuAg
fcc Sputtering AO (E) (111)
IrOsReRhRu hcp Thermal decomposition AO (E) (112)

Fig. 2. HEAs for thermocatalysis. (A) Schematic illustrating the carbothermal shock synthesis of the HEA nanoparticles (left) and temperature evolution during the
rapid heating-cooling process (right). (B) Schematic comparing the phase-separated heterostructures synthesized by a conventional method with slow kinetics and the
HEA nanoparticles prepared by the carbothermal shock approach. (C) Individual and low-magnification HAADF-STEM images with EDS element maps of octonary
(PtPdCoNiFeCuAuSn) nanoparticles (left). Scale bar, 10 nm. Atomically resolved HAADF-STEM image with the fast Fourier transform (FFT) pattern showing the fcc structure (right).
(A) to (C) are reproduced with permission from the American Association for the Advancement of Science (29). (D) Catalytic decomposition of ammonia using the RuRhCoNi
(Ru-4) MEA nanoparticles, Ru and RhCoNi catalysts (left), and two RuRhCoNiIr samples prepared by the carbothermal shock method (Ru-5 MEA-NPs) and the traditional
impregnation approach (Ru-5 IMP), respectively (right). (E) Performance comparison of the Ru-4 MEA and Ru-5 MEA nanoparticles with previously reported Ru-based
catalysts for ammonia decomposition. (D) and (E) are reproduced with permission from the American Association for the Advancement of Science (http://creativecommons.org/
licenses/by-nc/4.0/legalcode) (64). (F) Schematic illustration highlighting the rate-limiting factors in Co-rich (HEA-Co45Mo25), optimal (HEA-Co25Mo45), and Mo-rich
(HEA-Co15Mo55) catalysts for ammonia decomposition. Reproduced with permission from the Nature Publishing Group (http://creativecommons.org/licenses/by/4.0/) (67).

Mechanistic studies were performed to unveil the composition- that predicts the surface adsorption energies of the ORR intermedi-
dependent activities of the HEA-CoxMoy catalysts. According to the ates based on the local compositions. The authors calculated the
temperature-programmed desorption (TPD) results of the pre *OH and *O adsorption energies on a random subset of possible
adsorbed atomic nitrogen (2*N→N2), the HEA-CoxMoy catalysts surface binding sites on the (111) surface of the IrPdPtRhRu HEA. A
with higher Co/Mo ratios have lower values of the recombinative linear regression model was accordingly constructed and then ex-
desorption energy of nitrogen (EN). Plotting the ammonia decom- tended to the full span of the *OH and *O adsorption energies on all
position rate and activation energy versus the determined EN both the possible surface sites (Fig. 3A). The corresponding near-continuum
yield a volcano-type curve, indicating an optimal adsorption of distribution of the adsorption energies indicates that the position
atomic nitrogen with intermediate surface binding strengths results and intensity of the adsorption energy peak can be modulated and
in the best performance of ammonia decomposition. As illustrated potentially optimized through tailoring the surface composition of
in Fig. 2F, weak binding of atomic nitrogen on the Co-rich HEA- the HEA. Guided by the optimal *OH and *O adsorption energies,
CoxMoy catalyst induces a higher kinetic barrier for dehydrogenation Ir0.102Pd0.320Pt0.093Rh0.196Ru0.289 was predicted to have a ~40-mV
(NH3→*NH2→*NH→*N), while strong binding on the Mo-rich lower overpotential relative to that of Pt (111), which is the best
catalyst inhibits the recombination of atomic nitrogen to form pure metal surface for ORR. Interestingly, without constraining the
nitrogen molecules. Therefore, continuous tuning of the Co/Mo ra- number of the metal elements, the model predicted that Ir0.175Pt0.825
tio in the HEA-CoxMoy catalyst explores the vast compositional will be an even better ORR catalyst with a ~90-mV lower overpo-
space that is previously inaccessible in conventional Co-Mo binary tential compared with that of Pt (111). The results that go beyond

systems. Accordingly, the optimized surface with intermediate the multicomponent system demonstrate the universality of this
adsorption properties reaches a sweet spot between ammonia acti- computational model, which can function as an unbiased search
vation and recombination of atomic nitrogen, leading to maximized engine to discover high-performance ORR catalysts with optimal
reactivity for ammonia decomposition. elemental compositions.
The surface adsorption properties of HEAs are determined by
HEAs for electrocatalysis the ligand effect, which originated from the electronic perturbation
Electrocatalysis has played an ever-increasingly important role in from the metal species in the vicinity of the absorbate and the coor-
sustainable and clean energy conversions. The compositional and dination effect arising from the distinct local coordination environ-
structural diversity in HEAs permits continuous and enlarged tun- ments such as facets and atomic vacancies. The work from Rossmeisl
ing of the catalyst surface for efficient and selective electrochemical and colleagues studied the impact of elemental composition that
transformations. HEA electrocatalysts also afford a colorful palette mostly tunes the ligand effect, while both effects need to be consid-
to probe adsorption, activation, and conversion of molecular spe- ered to achieve a more accurate prediction. Regarding this, Lu et al.
cies bound to diverse surface sites. Systematic investigations, involv- (74) developed a neural network model based on DFT calculations
ing both experimental and theoretical efforts, have been conducted to simultaneously explicate both the ligand and coordination ef-
using HEAs to realize efficient and controlled electrochemical con- fects. This combined model allows universal prediction of the *OH
versions of small molecules such as H2O, O2, CO2, alcohol, etc. The adsorption energies on the surface sites of IrPdPtRhRu with 12 dif-
pronounced cooperative effects on the HEA surface could poten- ferent coordination structures. As shown in Fig. 3B, the general
tially break the scaling relationships for electrocatalysis, surpassing agreement between the experimentally measured activities and the
the long-established not-too-strong, not-too-weak guidance (68). computed adsorption energies validates the high accuracy of the
Oxygen reduction reaction prediction, which further permits decoupling of the ligand and co-
Oxygen reduction reaction (ORR) typically involves four proton- ordination effects. In addition, a number of composition and struc-
electron transfers to reduce oxygen to water (O2 + 4H+ + 4e− → 2H2O) ture factors including element identity, coordination number, neighbor
or two proton-electron transfers to produce hydrogen peroxide atom distance, etc., can be systematically investigated to navigate
(O2 + 2H+ + 2e− → H2O2) in acidic solutions. In alkaline media, the four- the optimal *OH adsorption manner.
electron pathway yields hydroxide ions (O2 + 2H2O + 4e− → 4OH−), Compared with the rapid progress of computational approaches,
whereas the two-electron process produces peroxide ions (O2 + H2O + the corresponding experimental development in exploring HEAs
2e− → HO2− + OH−) (69). The four-electron reaction is the cathode for ORR has lagged behind. This is mainly hindered by the lack of
reaction in fuel cells and thus has attracted extensive interests for high-efficiency synthetic and measurement tools to evaluate differ-
both fundamental and technological studies. The nonideal scaling ent HEAs. Hu and colleagues (75) developed the high-throughput
relations among multiple intermediates including O*, OH*, and synthesis of multimetallic nanoclusters (MMNCs) through modify-
OOH* induce an overpotential of 0.3 to 0.4 V even for the most ing the carbothermal shock technique. As illustrated in Fig. 3C,
active ORR catalysts such as Pt and Pd, which constitutes a large metal-salt precursors with desired recipes were dispersed onto car-
portion of the overall overpotentials for fuel cells (70). Therefore, bon support, which were further patterned on the copper plate.
substantially lowered overpotential, faster electrochemical kinetics, Rapid radiative heating allowed one-batch synthesis of up to 88
and reduced cost are desired for ideal ORR catalysts. MMNC samples with combinatorial elemental compositions, ranging
Previous studies have suggested that surface binding of the oxygen- from pure metals to quinary and octonary samples. For an expedited
containing intermediates with optimal strength has become a well- prescreening of the fabricated MMNC catalysts, the authors used
accepted criterion for the discovery and design of efficient ORR a scanning droplet cell setup where the copper substrate functions
catalysts (71, 72). While being used to rationalize the ORR activity as the current collector. The results showed that PtPdRhNi and
of unary and traditional alloys, this theory can hardly be applied to PtPdFeCoNi exhibited much higher ORR activities relative to that
HEAs owing to the inherent surface complexity. Moving a step for- of the Pt control, which was further validated using a prototypical
ward, Rossmeisl and colleagues (73) developed a predictive model rotating disk electrode. Another work by Ludwig and co-workers (76)


Fig. 3. HEAs for electrocatalysis. (A) Adsorption energies of *OH (left) and *O (right) based on DFT calculations, where each color represents an individual binding site.
Reproduced with permission from Elsevier (73). (B) Comparison between the predicted OH* adsorption energies and the experimentally measured ORR activities. Repro-
duced with permission from Elsevier (74). (C) Schematic illustration of the combinatorial and high-throughput synthesis of MMNCs. Reproduced with permission from the
National Academy of Sciences (https://creativecommons.org/licenses/by-nc-nd/4.0/) (75). (D) Comparison of the ORR activities (overpotentials at −0.5 V at normalized
scale) of individual, binary, ternary, and quinary alloy nanoparticles prepared by the ionic liquid–assisted cosputtering method. Reproduced with permission from
John Wiley and Sons (80). (E) The HER activities of the FeCoPdPtIr@GO synthesized by the FMBP method and loaded onto carbon paper (CP), Pt/C, and pure carbon
paper. Reproduced with permission from the Nature Publishing Group (http://creativecommons.org/licenses/by/4.0/) (30). (F) Anodic and cathodic polarization curves of
the CoFeLaNiPt HEMG catalyst and its individual components, all of which were prepared by the nanodroplet-mediated electrodeposition. Reproduced with permission
from the Nature Publishing Group (http://creativecommons.org/licenses/by/4.0/) (100). (G) Comparison of the specific activity of electrochemical methanol oxidation
using the HEA nanoparticles and the monometallic ones. The arrows show the scan directions of the cyclic voltammetry. Reproduced with permission from the American
Chemical Society (34).
demonstrated a closed-loop strategy that combines DFT calculation, To obtain monodisperse and freestanding HEA nanoparticles,
machine learning, combinatorial synthesis, and high-throughput Chen et al. (77) turned to colloidal synthesis. The authors prepared
measurement to the discovery of advanced electrocatalysts. With a intermetallic PdCu nanoparticles, upon which Pt, Ni, and Co were
machine learning model trained by a DFT dataset of *OH and *O simultaneously deposited on the surface via seed-mediated core-
binding energies, the authors interrogated the composition-dependent duction. Further annealing (600°C) of the PdCu@PtNiCo core@
ORR activity of the Ag─Ir─Pd─Pt─Ru HEA system. The identified shell architectures triggered atomic diffusion across the core/shell
HEAs with optimal adsorption properties were synthesized as thin interface, producing PdCuPtNiCo HEAs with well-retained nanopar-
films and measured using the scanning droplet cell. The obtained ticulate morphologies. The alkaline ORR performance of the HEA
results were further analyzed to refine the theoretical model, bring- exceeded that of the heterostructured PdCu@PtNiCo without an-
ing high prediction accuracies with iterative operations. These two nealing and the commercial Pt/C catalyst. Rotating ring-disk elec-
examples combining high-throughput synthesis and theoretical trode experiments indicated that oxygen is efficiently reduced on
predictions with rapid screening pipelines demonstrate the unprec- the surface of PdCuPtNiCo through the four-electron transfer path-
edented capability to achieve accelerated and potentially automatic way, which encompasses a lower ratio of peroxide relative to that of
materials discovery for high-performance HEA catalysts. the Pt/C catalyst. Moreover, stability tests revealed that Pt diffuses

out to form a Pt-rich skin that effectively prevents particle aggrega- (89) observed the formation of a metal-core/oxide-shell structure in
tion and structure degradation. The observed structure heterogeneity the nanoporous FeCoNiCrNb high-entropy intermetallic (HEI)
could be caused by the adsorbate-induced surface restructuring Laves phase. Compared with that of the state-of-the-art RuO2 refer-
under electrochemical conditions, and more work is anticipated to ence, this unique core-shell structure exhibited a higher OER activ-
elucidate the underlying mechanism. ity, faster kinetics, and advantageous stability in alkaline solutions.
Reducing the cost of the ORR catalyst is also important, especially In another study, Jin et al. (90) prepared a series of nanoporous
considering their integration into practical devices such as fuel cells AlNiCoIrM (M = Mo, Ni, V, Cu, and Cr) HEAs and applied electro-
and metal-air batteries. Several attempts have been made to prepare chemical activation process to introduce an Ir-rich surface. The
nanoporous HEA alloys with low Pt contents (78, 79). Schuhmann AlNiCoIrMo sample delivered a superior OER activity in acidic
and colleagues (80, 81) have systematically explored transition metal– media, exceeding the performance of commercial IrO2. Computa-
based HEA electrocatalysts for ORR, with a particular focus on un- tional investigations suggested that the increased covalency of the
derstanding the electrochemical behaviors on the multisite surface. Ir─O bond in the surface mixed oxide sites is the main contribution
Using an ionic liquid–assisted cosputtering method, the authors to the enhanced OER activity. Analogously, Qiu et al. (91) prepared
prepared the Cr─Mn─Fe─Co─Ni nanoparticles with the size less AlNiCoFeX (X = Mo, Nb, and Cr) nanostructures with oxide sur-
than 2 nm. The quinary HEA nanoparticles delivered an unex- face layers as alkaline OER catalysts, which were further integrated
pectedly high ORR activity, which is even comparable to the perform into the flexible direct ethanol fuel cells (92).
ance of Pt under the same conditions (Fig. 3D). Furthermore, The appealing performances of HEAs functioning as both ORR

adjusting the Mn content in the Cr─Mn─Fe─Co─Ni system mea- and OER catalysts have spurred interests in the application of bi-
surably modulated the ORR activity, which was further elaborated functional oxygen electrocatalysts. This is particularly useful for
by using the inflection points of the voltammetric activity curves as metal-air batteries, which involve ORR during discharge and OER
the activity descriptor for ORR (82). during charge. Using the carbothermal shock method, Hu and
Despite the success in applying transition metal–based HEA cat- co-workers (93) synthesized a set of multimetallic nanoparticles for
alysts for efficient ORR, little has been known considering how to aprotic oxygen catalysis in Li-O2 batteries. They found that the
interpret and predict the corresponding electrochemical activity stability of the electrocatalyst is closely related with the configura-
curve. For unary or conventional alloyed electrocatalysts, one po- tional entropy. With comparable activities, the octonary sample
larization curve is typically yielded in voltametric activity measure- (RuIrCeNiWCuCrCo) outperformed the quaternary one (RuIrCeNi)
ment. In contrast, the HEA catalysts exhibit a combination of in long-term operation, and the performance of the quaternary one
several curves, corresponding to the diverse active sites with similar exceeded that of the binary (RuIr) one. In comparison, the phase-
binding energies (83). With a simplified model, Schuhmann and segregated multimetallic catalysts synthesized using the wet im-
colleagues managed to simulate the ORR activity curve in the pregnation approach suffered from severe oxidative degradation.
Cr─Mn─Fe─Co─Ni system. Further experimental results showed Fang et al. (94) integrated the noble metal–free HEAs in aqueous
that the HEA catalysts containing five or more elements outper- Zn-air batteries and demonstrated the as-formed multicomponent
formed the corresponding binary, ternary, and quaternary alloys in surface oxides with favorable eg occupancy and optimal covalency
alkaline media. The broad adsorption energy distribution of the of the metal-oxygen bond impart the enhanced electrochemical ac-
HEA catalysts partially covers more optimal binding energies for tivity and stability.
the intermediates, hence markedly boosting the ORR activity. This Hydrogen evolution reaction
body of work from Schuhmann and colleagues affords a distinct As the other half-reaction for electrocatalytic water splitting, hydrogen
route toward understanding the interrelationships among compo- evolution reaction (HER) involves two proton-coupled electron trans-
sition control, modification of surface adsorption of the ORR inter- fers (2H+ + 2e− → H2 in acidic media and 2H2O + 2e− → H2 + 2OH−
mediates, and tuning of the electrochemical behaviors. The developed in alkaline solutions) and only one intermediate species (H*) in the
concept can be further extended to optimization of the catalyst sta- rate-determining step. The volcano plot describing the hydrogen
bility, which is important for the design of robust noble metal–free adsorption free energy (GH) on metal surfaces indicates that an
ORR catalysts. active HER catalyst requires an optimal binding to the reaction inter-
Oxygen evolution reaction mediate that is neither too strong nor too weak. With an almost ther-
Similar to ORR, oxygen evolution reaction (OER) also involves four moneutral GH, Pt proves to be the most active HER catalyst that
proton-coupled electron transfers with sluggish kinetics but based requires minimal overpotential to achieve high hydrogen production
on the half-reactions where molecular oxygen is produced in acidic rates in acidic solutions (70). HER has therefore been primarily ap-
(2H2O → O2 + 4H+ + 4e−) or alkaline media (4OH− → O2 + plied as a model reaction to develop feasible synthetic techniques and
2H2O + 4e−). To take advantage of the highly tunable surface prop- probe structure-function relationships of nanostructured HEAs.
erties, researchers have investigated bulk and nanostructured HEAs The abovementioned carbothermal shock method can be used
as OER catalysts (84–86). Contrary to the reducing conditions in to fabricate HEA nanoparticles supported on carbon nanofibers,
ORR, the high positive potentials required for OER tend to oxidize while the applied joule heating can hardly be extended to catalyst
the surface of the metal catalysts and form metal oxides or (oxy) supports with poor electrical conductivities. Gao et al. (30) developed
hydroxides (87). Recent studies have revealed that oxidation of a facile FMBP technique to overcome this issue. During synthesis,
HEAs is governed by the Kirkendall effects (88), where the metal moving the supported precursors into the heating zone triggers rapid
atoms diffuse outward and form disordered oxidation layers. It is temperature increase (reaching 923 K within 5 s). The instant pyroly-
thereby important to note that in most cases, the active sites of the sis results in formation of the HEA nanoparticles containing up to
HEA catalysts for OER are the restructured oxide or (oxy)hydrox- 10 elements (MnCoNiCuRhPdSnIrPtAu). In contrast, the traditional
ide surface layers instead of the original metallic phase. Ding et al. fixed bed pyrolysis produces phase-separated heterostructures

owing to a much slower heating rate (20 K/min). This approach can the authors successfully governed the localized nucleation and
be readily extended to substrates with poor electrical conductivities, domain growth. This electroshock synthesis strategy shares the same
including graphene oxide (GO), -Al2O3, and zeolite. With elec- merit of kinetic control with the carbothermal shock approach.
tronic modulation via inclusion of Fe, Co, and Pd, the GO-supported Nonetheless, the room temperature operation cannot provide enough
quinary HEA nanoparticles (FeCoPdIrPt) exhibited enhanced HER energy to overcome the thermodynamic barrier to crystallization,
activity and stability in alkaline solutions relative to that of the com- thus yielding amorphous structures with homogeneous yet random
mercial Pt/C catalysts (Fig. 3E). In another research, Dai and col- atomic distributions. The quinary CoFeLaNiPt HEMG nanoparticles
leagues (95) took advantage of the acoustic cavitation and achieved exhibited advantageous activity and stability functioning as both
atomic mixing of different metal species under ambient conditions. HER and OER catalysts, which is promising to drive overall water
These synthetic methods share the same merit with the carbother- splitting (Fig. 3F).
mal shock technique, where different metal atoms are mixed and Carbon dioxide reduction
kinetically trapped during the nonequilibrium process. Another key reaction for energy conversion is the electroreduction
Mechanistic insights have also been revealed to uncover the elec- of carbon dioxide, where CO2 is electrochemically reduced to valu-
tronic structures of nanostructured HEAs. The d-band theory, which able chemicals and fuels. CO2 electrochemical reduction also in-
has been widely used to rationalize the HER performance of unary volves multielectron transfers that are similar to ORR but yields a
and binary noble metal electrocatalysts (96), can hardly be applied much broader scope of products including C1 products (carbon
to HEAs because of the strong synergy among different metals. To monoxide, formate, formaldehyde, methane, methanol, etc.), C2+

bridge this gap, Kitagawa and co-workers (97) examined the link be- hydrocarbons and oxygenates, and heteroatom-containing chemi-
tween the electronic structure and the HER activity of the HEA catalyst. cals (70, 101). Meanwhile, the simultaneous HER process in aqueous
Hard X-ray photoelectron spectroscopy (HAXPES) was deployed to solutions also produces the unwanted H2 as the competing biproduct.
probe the valence band structure of the IrPdPtRhRu HEA nanopar- Fabricating highly efficient and selective CO2 reduction catalysts
ticles, which exhibited measurably higher HER activities in both acidic toward value-added commodities is thereby greatly desired and has
and alkaline solutions compared with that of the monometallic cata- been actively pursued.
lyst and even the commercial Pt catalyst. The measured broad valence Rossmeisl and colleagues (102) investigated electrochemical CO2
band spectrum of the HEA nanoparticles renders direct evidence for and CO reduction on the HEA surface by combining DFT with
the hybridization of the metal orbitals. Interestingly, further analysis supervised machine learning. The (111) facets of two quinary fcc
showed that the HEA catalyst does not follow the well-known cor- HEAs, CoCuGaNiZn and AgAuCuPdPt, were chosen as the model
relation between the turnover frequency and the position of the ex- systems. With the Gaussian process regression trained with the
perimental d-band center. This deviation may originate from the DFT-calculated adsorption energies of H and CO, the authors were
complex atomic arrangements and corresponding diverse local den- able to assess the likelihood of yielding multicarbon products on all
sity of states on the HEA surface, indicating a potentially powerful the possible surface microstructures. Further analysis illustrated the
route to surpassing the linear scaling relationship (68). correlation between composition tuning and modulation of the CO
More broadly defined HEAs with varied structure orders, micro- and H adsorption energies, together with the trade-offs between
structures, and crystallinities have also been explored to catalyze activity and selectivity. On the basis of the criteria of weak H ad-
HER. Jia et al. (98) combined the intrinsic site-isolation effect in sorption and strong CO adsorption, the authors identified binary
intermetallics and strong chemical synergy in HEAs and fabricated GaNi as a locally optimal candidate, which was further experimen-
a multinary HEI catalyst. The designed dual-phase FeCoNiAlTi tally verified.
HEI alloy displayed a dendritic L12 phase, where the Al and Ti atoms Complementary to the computational predictions, Nellaiappan et al.
occupy the vertices and the Fe, Co, and Ni atoms settle on the face (103) applied nanocrystalline AuAgPtPdCu HEAs for the electro-
centers. DFT calculations suggest that the Ti atoms with strong catalytic conversion of CO2. The Cu species with the Cu2+/Cu0 re-
adsorption energies facilitate H2O adsorption, whereas the isolated dox pair was determined as the main active site for CO2 reduction,
Al atoms coordinating with Fe, Co, or Ni provide a beneficial GH whereas the other spectator components contribute to electronic
for efficient adsorption and desorption of H*. In this way, the con- and structural regulation of the single-atom Cu sites. At low over-
version of both reactant (H2O) and intermediate (H*) are promoted, potentials [−0.3 V versus reversible hydrogen electrode (RHE)],
collectively leading to enhanced HER performances that are superior the HEA catalyst converts nearly all the CO2 to gaseous products
to those of Pt. Yao et al. (99) fabricated a monolithic nanoporous (38.0% CH4, 29.5% C2H4, 4.0% CO, and 26.4% H2), which was
CuAlNiMoFe electrode using a facile and scalable alloying/dealloying attributed to the modification of the O* and CH3O* adsorption
approach. The electroactive multielemental CuNiMoFe surface is in energies on the HEA surface according to DFT calculations. It is
situ formed on the body-centered cubic (bcc) CuAlNiMoFe precip- worth pointing out that much is still unknown about the exact
itates, which are seamlessly anchored on the Cu skeletons. The behaviors of the CO2 reduction intermediates on the HEA surface.
entropy-stabilized surface containing atomically mixed Cu, Ni, Mo, For instance, noticeable CO2 reduction activities were observed for
and Fe species facilitates H* adsorption and desorption, whereas the AuAgPtPdCu catalyst in the CO2-saturated K2SO4 solutions,
the nanoporous Cu skeleton serves as an ideal current collector for but not in the CO2-saturated NaHCO3 electrolytes that have been
electrical conduction as well as a robust morphological template commonly used. This unconventional feature can be useful for the
that promotes the transport of ionic and molecular species for design of pH-dependent electrocatalysts. Meanwhile, continuous
HER. High-entropy metallic glasses (HEMGs) with low crystallini- tuning of the active sites on the HEA surface may favor cascade
ties have also been fabricated by Glasscott et al. (100) using reactions where the intermediates produced on the neighboring
nanodroplet-mediated electrodeposition. By confining the metal sites react with each other through C─C coupling and promote the
salt precursors to water nanodroplets suspended in dichloroethane, formation of higher-value chemicals.

Alcohol oxidation (112) for electrocatalytic oxidation of alcohol. Moreover, the authors
As one of the most promising electrochemical setups to power elec- realized phase tuning by modifying the elemental compositions. For
tric vehicles, fuel cells enable continuous supply of electricity con- instance, Ir0.19Os0.22Re0.21Rh0.20Ru0.19 has the hcp structure, whereas
verted from the chemical energy of fuels. Direct alcohol fuel cells Ir0.26Os0.05Pt0.31Rh0.23Ru0.15 crystalizes in the fcc manner. This pro-
(DAFCs) are advantageous compared with the hydrogen-fed ones vides a starting point to understand polymorphism in HEAs, which
because of the higher volumetric density and convenience in stor- has been somewhat limited due to the prevalence of the fcc-structured
age and transport (104). Methanol and ethanol are two common HEAs (Table 1).
fuels for DAFCs. The excellent corrosion resistance and strong syn- Summary of HEAs for catalysis
ergistic effects make HEAs promising catalysts to catalyze efficient To summarize, HEAs have shown enhanced performances catalyz-
and complete oxidations of the alcohol fuels. ing various thermal and electrochemical reactions. The advantageous
The platinum-group metals (PGMs), including Ru, Rh, Pd, Os, catalytic properties of HEAs can be ascribed to the wider composi-
Ir, and Pt, have been extensively used as electrocatalysts for alcohol tional tuning range, which even surpasses the miscibility limitation
oxidations. While simple reactions can be triggered by mono- and for conventional alloys. Confining five or more metal species at the
bimetallic PGMs, it is difficult to drive complex reactions involving atomic scale synergistically modifies the electronic and geometric
multiple proton-electron transfers and intermediate species. Kitagawa characteristics on the HEA surface. The diverse surface sites ac-
and co-workers (34) applied the PGM-HEA nanoparticles for elec- cordingly introduce a wide scope of adsorption energies for the
trocatalytic ethanol oxidation that involves as many as 12 proton- intermediates, bringing more opportunities for modulating the ac-

electron transfers. The PGM-HEA nanoparticles were prepared tivity and selectivity. This is particularly useful for optimizing reac-
using a facile polyol method. As illustrated in Fig. 3G, the PGM-HEA tions that involve multiple charge transfers, such as electrochemical
nanoparticles efficiently catalyzed the ethanol oxidation reaction, CO2 reduction and alcohol oxidation. The microstructure of the
exhibiting a much higher activity relative to that of the commercial HEA catalysts also plays an important role, where higher surface
Pd/C, Pd black, and Pt/C catalysts, respectively. In stark contrast, area and robust metal/support interfaces are desired. In addition,
negligible activity was observed for the physical mixture of the six the improved catalytic stability of HEAs, which has been taken for
unary PGM nanoparticles. The PGM-HEA also delivered a mass granted as a result of the entropy-induced stabilizations, can be a
activity more than 1.5 times higher than that of the most active cat- complicated topic and requires more investigations. Recent studies
alyst to date (Au@PtIr/C). Moreover, compared with the ternary, have revealed that HEAs are not impervious under electrochemical
quaternary, and quinary PGM alloys, the PGM-HEA exhibited the reactions (77), and the associated surface restructuring can be either
highest current density in the full potential range, reflecting its beneficial or harmful. Understanding retention and reconstruction
enhanced capability to efficiently catalyze oxidation of multiple of the surface and subsurface structures, which vary according to
intermediates. To better understand the contribution of each metal, different reaction environments (liquid and gas phases) and driving
the authors compared the cyclic voltammetry curves of each indi- forces (thermal and electrochemical reactions), is thereby import-
vidual constituent in the presence and absence of ethanol. Pt and Pd ant to clarify the catalytic behaviors of the HEAs.
are active for ethanol conversion but become poisoned by the
adsorbed (CO)ad or CHx species. Os and Ru, although not directly
active for ethanol conversion, facilitate oxidation of (CO)ad and HEOs FOR CATALYSIS
thus mitigate the poisoning effect for Pt and Pd. Ir and Ru ensure In 2015, Maria and colleagues (113) reported the entropy-induced
that dehydrogenation or C─C cleavage occurs at a low potential, stabilization of single-phase multicomponent oxides, in which Mg,
while further oxidation hinges on the Pt and Pd components. The Ni, Zn, Cu, and Co are randomly distributed in the rock salt oxide
atomically mixed metals in HEAs play distinct yet concerted func- lattice (Fig. 4A). Since then, studies have unveiled more and more
tions that give rise to efficient and complete oxidation of ethanol. exotic properties for HEOs. Distinct from HEAs mostly having single-
Alloying PGMs with transition metal elements is another route site occupancies in the fcc structure, HEOs have independent cation
to increasing the alcohol oxidation capability. Feng et al. (105) used and anion sublattices that give rise to increased structural diversi-
a sparking mashup technique to fabricate up to 55 alloy nanoparti- ties (114). Therefore, in addition to the expanded tuning range in
cles ranging from binary alloys to HEAs. The as-synthesized Pt and composition and structure, elucidating the impact of the increased
Pd alloys displayed enhanced performances for the electrochemical entropic effects on the oxygen part, especially activation of lattice
oxidation of methanol, ethanol, and formic acid. Alloying Pt (or Pd) oxygen, has become the focus point for HEO-based catalysts. The
with other metal species modulates the electronic structure and ability to create and control oxygen defects in various HEO struc-
weakens the binding of the CO-like intermediates and thus allevi- tures is particularly useful for increasing the catalytic activity of var-
ates the related poisoning effect. In another study, Li et al. (106) ious oxidation reactions.
prepared the Pt18Ni26Fe15Co14Cu27 HEA nanoparticles, which ex- The catalytic applications based on HEOs can be mainly divided
hibited remarkable methanol oxidation activities and enhanced CO into two categories. The first is to directly apply HEOs as catalysts,
antipoisoning in alkaline solutions. Using DFT calculations, the where the entropy-stabilized aliovalent cations lead to unique de-
authors analyzed the partial projected density of states of each ele- fect features and adjustable electronic properties in high-entropy
ment upon methanol adsorption and revealed an efficient site-to-site rock salt, fluorite, and perovskite oxides (Fig. 4B). The oxide lattice
electron transfer process. This multisite HEA catalyst also showed affords a dynamic matrix to buffer the structural distortions among
superior activity and stability for HER in alkaline solutions (107) different cationic species. The second is to apply HEOs as robust
and pH-universal nitrogen reduction (108). In addition to HEAs supports to anchor the transition metal and noble metal active spe-
with the fcc structure (109–111), the one having the hexagonal close- cies. Probing the corresponding metal-support interactions affords
packed (hcp) structure has also been synthesized by Yusenko et al. more insights into the enthalpy-entropy correlations based on


Fig. 4. HEOs for catalysis. (A) XRD patterns showing the structure evolution of the equal molar mixture of MgO, NiO, ZnO, CuO, and CoO annealed in air at different
temperatures. The diffraction peaks corresponding to the non–rock salt impurity phases are highlighted using arrows. Reproduced with permission from the Nature
Publishing Group (http://creativecommons.org/licenses/by/4.0/) (113). (B) Schematics displaying the structures of the high-entropy rock salt, fluorite, and perovskite
oxides. Oxygen atoms are in red, and the high-entropy metal sites are in blue/white. A and B sites in the perovskite oxide structures are highlighted in blue/white and
green/white, respectively. (C) In situ Cu L2,3 edge XAS spectra of the Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O catalyst in CO at 235°C (red to blue with a 60-min interval) and then
switched to the O2 atmosphere at the same temperature (black). Reproduced with permission from the American Chemical Society (48). (D) Thermochemical water splitting
performance of (FeMgCoNi)Ox, NiFe2O4, and CoFe2O4 and the calculated thermodynamic limit of CeO2. Reproduced with permission from the Royal Society of Chemistry
(121). (E) Methane oxidation performance of 10-MEO-PdO, (Zr,Ce)0.6Mg0.3Pd0.1Ox (4-MEO-Pd), and PdOx supported on carbon paper at 648 K under dry conditions. Repro-
duced with permission from the Nature Publishing Group (37). (F) Schematic illustration for the mechanochemical synthesis of single Pd atoms supported on (CeZrHfTiLa)
Ox and Pd clusters anchored on CeO2. Reproduced with permission from the Nature Publishing Group (http://creativecommons.org/licenses/by/4.0/) (31). (G) Temperature-
dependent XRD patterns of the Au-HEO sample switched between 700° and 900°C (left) and the magnified in situ XRD intensity map in the first cycle heated from 700° to
900°C (right). Reproduced with permission from the Royal Society of Chemistry (126). a.u., arbitrary units.
HEOs, which can be sometimes counterintuitive yet potentially power- the oxide lattice fosters lattice oxygen activation in the form of defects.
ful. In either case, understanding activation, stabilization, and migra- However, extreme synthetic conditions including elevated tem-
tion of oxygen species on the surface and in bulk of HEOs is crucial, peratures and high pressures frequently produce bulk samples with
which will be discussed and compared in this section (Table 2). low surface areas. Oxygen partial pressure has also been demon-
strated as an important factor that contributes to the formation of
HEOs as catalysts HEOs (37). Multiple synthetic strategies have thereby been tailored
HEOs with common rock salt and fluorite structures are appealing to access nanostructured HEOs for diverse catalytic reactions.
targets for thermocatalysis. Modified Jahn-Teller effects of the metal Selective oxidation of benzyl alcohol to benzaldehyde, benzoic acid,
cations induce distorted structural and modified electronic features. and benzyl benzoate has drawn wide interests to provide essential
Homogeneous and random distribution of the aliovalent cations in intermediates for the manufacture of medicines and agrochemicals.

Feng et al. (8) found that a holey lamellar HEO catalyst has high structure supported on the sponge-like alumina nanoarchitectures.
activity for the solvent-free aerobic oxidation of benzyl alcohol. CO oxidation was performed to evaluate the catalytic properties of
Using an anchoring and merging strategy, the authors prepared the the mesoporous unary metal oxide–Al2O3 and the HEO-Al2O3 hy-
rock salt Co0.2Ni0.2Cu0.2Mg0.2Zn0.2O HEO with a holey lamellar ar- brids. CuO-Al2O3 and HEO-Al2O3 exhibited the best activities with
chitecture. Structural reversibility between the multiphase state at the T100 values of 220° and 260°C, respectively. Upon treatment in
750°C and the single-phase at 900°C was monitored by the corre- 1000 parts per million of SO2, the activity of CuO-Al2O3 markedly
sponding XRD patterns, which is important to demonstrate the dropped, while the performance of HEO-Al2O3 remained almost
entropy-induced transitions. The holey lamellar HEO was applied unaltered. The rock salt HEO phase thus displayed a noteworthy
for aerobic oxidation of benzyl alcohol to benzoic acid and exhibited enhancement in sulfur resistance in CO oxidations, which is of vital
up to 98% conversion in 2 hours under the solvent-free atmospheric significance for industrial processes.
conditions. The bulk HEO counterpart as well as the arbitrary unary, Although the metal cations randomly distributed in the HEO
binary, ternary, and quaternary counterparts exhibited a much lower lattice can be viewed structurally equivalent, their roles in catalytic
activity. Further investigation revealed that the holey HEO pro- reactions vary. Some function as active sites that account for the
motes formation of oxygen vacancies due to the small domain size, adsorption and conversion of molecular species, while the others
random substitution of multiple metal cations, and oxygen con- act as neighboring spectators that permit electronic or geometric
sumption during the burning off of the GO support. The enriched regulation. To identify the active species in the rock salt HEO
oxygen vacancies on the holey HEO lead to enhanced oxygen deliv- (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O) for CO oxidation, Fracchia et al. (48)

ery capacities and stronger adsorption to benzyl alcohol molecules used operando soft XAS to monitor the evolution of the L2,3 edge of Cu,
relative to that of the bulk counterpart, giving rise to efficient mo- Co, and Ni in different atmospheres. While XAS is typically consid-
lecular conversions. The rock salt MoNiCuZnCoOx has also been used ered as a bulk technique, the total electron yield mode endows the
for oxidative desulfurization oxides (115), which is a crucial process capability to probe the 3d states of the transition metal species on
to eliminate sulfur contents in fossil fuels. The uniformly dispersed the surface and subsurface regions, which is particularly useful for
Mo6+ species and efficient activation of lattice oxygen in the HEOs catalytic studies. The authors found that Cu(II) in the HEO could
facilitate an enhanced conversion of the thiophene derivatives com- be reduced to Cu(I) by CO at a temperature higher than 130°C
pared with that of the Mo-based binary and ternary oxides. (Fig. 4C), whereas Co and Ni remain unaltered under the same con-
Mesoporous metal oxides with tunable pore sizes, structures, dition. This makes sense since Cu is the most anomalous one among the
and compositions are attractive for catalytic applications. Dai and five elements taking the size- and structure-related and electronic
co-workers (116) presented a facile mechanochemistry-assisted effects into consideration (114). The Cu site was accordingly identified
synthesis route of the mesoporous CuNiFeCoMgOx-Al2O3 hybrids. as the main active site for CO adsorption and oxidation. Moreover, the
Metal precursors including aluminum isopropoxide and anhydrous rock salt HEO exhibited a higher tolerance against reduction com-
metal chlorides, together with tunable soft templates, were intro- pared with that of CuO. This underscores the role of the increased
duced to the ball milling process. The as-obtained precursor was configurational entropy in stabilizing Cu(II) in the cubic structure
then calcinated, resulting in the formation of the rock salt HEO rather than transforming back to the original monoclinic structure.
Table 2. Summary of HEOs for thermocatalysis, electrocatalysis, and photocatalysis. T, thermocatalysis; E, electrocatalysis; P, photocatalysis.
Rock salt Template method Aerobic oxidation of benzyl alcohol (T) (8)
NiMgCuZnCoOx
Rock salt Solid-state synthesis CO oxidation (T) (48)
MoNiCuZnCoOx Rock salt Solid-state synthesis Oxidative desulfurization (T) (115)
Nonhydrolytic sol-gel
NiMgCuFeCoOx-Al2O3 Rock salt + amorphous (binary) CO oxidation (T) (116)
strategy + ball milling
CuCeOx-NiMgCuZnCoOx Fluorite + rock salt (binary) Ball milling CO oxidation (T) (117)
Monoclinic + orthorhombic
TiZrHfNbTaO11 High-pressure torsion HER (P) (119)
(binary)
(CoCuFeMnNi)3O4 Spinel Solvothermal synthesis OER (E) (120)
FeMgCoNiOx Spinel + rock salt Sol-gel + solid-state synthesis Water splitting (T) (121)
Coprecipitation +
Pt1/NiMgCuZnCoOx Rock salt CO oxidation (T) (122)
solid-state synthesis
Ru/NiMgCuZnCoOx and Pt/
hcp/rock salt and fcc/rock salt Ball milling CO2 hydrogenation (T) (123)
NiMgCuZnCoOx
Ru/BaSrBi(ZrHfTiFe)O3 Perovskite Sonochemical synthesis CO oxidation (T) (124)
ZrCeMgLaYHfTiCrMnPdOx Fluorite Carbothermal shock Methane combustion (T) (37)
Pd1/CeZrHfTiLaOx Fluorite Ball milling + calcination CO oxidation (T) (31)
Au/NiMgCuZnCoOx fcc/rock salt Solid-state synthesis CO oxidation (T) (126)

Ceria-based fluorite oxides have also been revisited to initiate a roles in maximizing the thermocatalytic conversion with low TH, as
series of entropy-centered discussions. According to the Gibbs free well as stabilizing the metal oxide phase. The authors combined sol-
energy equation, the enhanced entropic contributions at higher gel and solid-state methods to prepare the (FeMgCoNi)Ox PCO
temperatures may compensate more of the enthalpic effects, giving with coexisting rock salt and spinel phases. The performance of the
rise to higher stabilities under harsh operating conditions. Dai and (FeMgCoNi)Ox catalyst exceeded that of the previously reported ma-
colleagues (117) reported a mechanochemical strategy to fabricate terials, including spinel ferrites, substituted ceria, and Mn-based per-
heterostructured, ultrastable CuCeOx-HEO catalysts. CeO2 and ovskite oxides (Fig. 4D). XANES data of the quenched (FeMgCoNi)Ox
HEO (MgZnCoCuNiOx) were individually prepared and then mixed sample suggested that Fe is the only redox active element, while
for ball milling. Driven by the mechanochemistry-induced short- the role of the other spectator species remains elusive. Dynamic in-
range high temperatures, Cu and Zn migrated from the HEO do- teractions across the interface between the rock salt and spinel do-
main into the CeO2 lattice and formed CuZnCeOx solid solutions. mains and localized heating effects promote the thermochemical
Directly annealing the mixture of the cerium and metal precursors production of hydrogen, which can be integrated into large-scale
would only produce metal oxides deposited on the CeO2 surface. chemical infrastructures. Strictly speaking, (FeMgCoNi)Ox does
CuCeOx-HEO exhibited an outstanding high-temperature stability not fall in the category of HEMs since there are less than five prin-
as almost no activity degradation was observed after calcination at cipal components. However, the enthalpy-entropy correlations can
900°C. The HEO functions as a stabilized reservoir, which provides still be exploited as a versatile guideline to improve the catalytic
abundant Cu species that migrate across the oxide-oxide interface performances.

and form the stable CuCeOx structure. In contrast, CuO-CeO2
showed a marked activity deterioration after the treatment at 900°C, HEOs as supports
demonstrating the key role of the entropy-induced structure recon- The excellent chemical and thermal stabilities and favorable forma-
struction at the oxide-oxide interface. Using a similar process, tion of oxygen defects render HEOs as attractive candidates for cat-
Shu et al. (9) overcame the intrinsic solubility limitation of the alio- alyst supports. Noble metal species with various sizes, ranging from
valent metal cations in the fluorite structure. The authors simulta- nanoparticles to atomic clusters and single atoms, have been an-
neously incorporated 10 mole percent (mol %) Cu2+, 10 mol % Co2+, chored on HEOs. In a pioneering study, Dai and colleagues (122)
10 mol % Mg2+, 10 mol % Ni2+, and 10 mol % Zn2+ cations into the deposited 0.3 weight % (wt %) of single Pt atoms on the rock salt
CeO2 lattice, which facilitate the formation of the vacancy-mediated NiMgCuZnCoOx through a codeposition approach. Thermal treat-
reactive oxygen species as well as local lattice distortion. With di- ment at 900°C induced the formation of the surface-confined
verse surface sites that alleviate competitive adsorption of different Pt─O─M bonds (M represents Ni, Mg, Cu, Zn, and Co). A subse-
gaseous components, the entropy-stabilized multicomponent CeO2 quent reduction step with H2 converted the O─Pt─O─M (Pt4+) to
catalysts permitted efficient treatment of CO-toluene-propylene the Pt─O─M (Pt2+) bonds, creating active sites for CO oxidation.
and typical automotive exhaust and displayed enhanced thermal No activity loss was observed for PtNiMgCuZnCoOx for 40 hours at
and hydrothermal stabilities. 135°C, validating the appealing thermal and chemical stabilities of the
Perovskite oxides are another class of appealing oxides because HEO-supported catalysts. Following this work, Dai and co-workers
of the intrinsic dual-site cation occupancy and common oxygen have developed various synthetic routes toward HEO-supported
nonstoichiometry (118). High-entropy perovskite oxides (HEPOs), noble metal catalysts under mild operating conditions. Leveraging
where both A and B sites can be filled with different sets of metal the high local temperature induced by ball milling, the authors in-
cations, afford flexible electronic and physiochemical properties for corporated up to 5 wt % of noble metal species as a combination of
catalytic applications. Using mechanical alloying followed by high- single atoms and nanoclusters onto the NiMgCuZnCoOx support
temperature oxidation, Edalati et al. (119) prepared a two-phase (123). 5 wt % of Ru and Pt, when loaded onto the HEO support, both
HEPO composed of 60 mol % of the monoclinic phase (AB2O7) and exhibited enhanced activity, selectivity, and high-temperature stability
40 mol % of the orthorhombic structure (A6B2O17), where A rep- for selective hydrogenation from CO2 to CO. In addition, Dai and
resents Ti, Zr, and Hf, and B represents Nb and Ta. With an overall co-workers (124) applied sonochemistry to fabricate high–surface
composition of TiZrHfNbTaO11, this binary HEPO had a main area HEPOs to stabilize noble metal catalysts for CO oxidation. The
bandgap of 2.9 eV and exhibited good light absorbance in both ul- acoustic cavitation causes formation, successive growth, and implosive
traviolet and visible-light regions, in stark contrast to the negligible collapse of microscopic bubbles, generating massive energy with local
light absorbance for the individual metal oxide component. The temperatures above 5000°C and pressures exceeding 2000 atm on a
tunable electronic properties derived from the d0 configuration time scale of ≤10−9 s. The resulted local extreme conditions drove a
together with the enhanced light absorbance in the visible-light homogeneous mixing of different metal atoms and consequent for-
range give rise to efficient photocatalytic water splitting. In another mation of the single-phase crystalline HEPO.
study, Wang et al. (120) fabricated spinel (Co, Cu, Fe, Mn, Ni)3O4 A recent breakthrough from Hu and colleagues (37) afforded
nanoparticles anchored on carbon nanotubes as efficient alkaline well-defined guidelines to access multielement oxide (MEO) nanopar-
OER electrocatalysts. ticles. On the basis of the carbothermal shock technique, the au-
Zhai et al. (121) extended the cation-mixing strategy to a broader thors systematically studied the impact of temperature, oxidation,
class of metal oxides, polycation oxides (PCOs), to catalyze two- and entropy in the formation of single-phase MEO nanoparticles
step thermochemical water splitting (TWS) reactions. During this with rock salt, fluorite, spinel, and perovskite structures. Increasing
two-step process, metal oxides undergo a redox cycle, releasing the synthetic temperature and oxygen partial pressure and incorpo-
oxygen at high temperatures (TH), and then get oxidized when trig- rating more metal cations were shown to favor the formation of the
gering the thermochemical steam-to-H2 conversion at lower tem- single-phase MEO nanoparticles ranging from unary to denary com-
peratures (TL). The partial molar entropy and enthalpy play crucial positions. An efficient designing scheme was further demonstrated to

optimize the nanostructured MEO catalysts for methane combustion. and the underlying HEO support. The self-regenerative phenomenon
Alkali metals promoting the electron transfer, 3d-5d transition metals paves the way toward robust deposition of noble metal catalysts for
improving the redox properties through oxygen vacancy formation, high-temperature reactions. Entropy-favored construction of isolated
and noble metal Pd that facilitates methane activation were opti- atomic species instead of nanoscale particles also brings a funda-
mized through a step-by-step screening process. The optimal denary mentally distinct pathway toward solving issues such as sintering,
(Zr,Ce)0.6(Mg,La,Y,Hf,Ti,Cr,Mn)0.3Pd0.1O2–x catalyst exhibited enhanced coking, and poisoning (127).
activity and stability when compared to the PdOx and quinary catalysts Summary of HEOs for catalysis
(Fig. 4E), which was attributed to the entropy-induced stabilization Introduction of the oxide lattice screens the entropic interactions
of Pd in a cationic state. The enriched library of MEO nanoparticles among the metal cations, permitting independent cationic and
prepared using generalizable protocols promises great potential to anionic stabilizations. In addition to the expanded range in compo-
build high-performance catalysts for expanded catalytic reactions. sition and structure, the involvement of oxygen species in multiple
Stabilizing noble metal atomic species on the oxide support is forms switches the research focus to oxidation reactions. Leverag-
important to realize sustainable and efficient catalytic conversions. ing the entropic effects in HEOs to facilitate generation of active
However, the relatively low Tammann temperature, the point at oxygen species under mild conditions has become the main mo-
which noble metal species develop liquid-like behaviors and migrate mentum. The enhanced configurational entropy provides a distinct
on the oxide surface, leads to sintering of the catalysts and activity route to activating lattice oxygen through compensating the enthal-
degradation (125). As an unconventional stabilization strategy, the pic gains. In parallel, the metal part functions as the adsorption site

enhanced entropic contributions would hypothetically favor the for small molecules (CO, CO2, CH4, and H2O), ions (H+ and OH−),
incorporation of foreign atoms into the underlying oxide structure. and organic hydrocarbons. Applying HEOs as catalyst supports
Dai and co-workers (31) demonstrated the entropy-driven stabili- shares the same merit of lattice oxygen activation, whereas the
zation of Pd single-atom catalysts (SACs) on the high-entropy fluorite anchored noble metal species become the active sites. Anchoring
oxides (HEFOs). As illustrated in Fig. 4F, the authors combined single metal atoms on HEOs has blurred the boundary between
mechanical milling with high-temperature calcination to fabricate catalyst and catalyst supports, affording a conceptually distinct
(PdyCeZrHfTiLa)Ox solid solutions, where Pd formed Pd─O─M alternative to robust SACs.
bonds (M = Ce, Zr, Hf, Ti, and La) through cation substitution in Another key difference between HEA and HEO catalysts is the
the fluorite structure. In contrast, segregated Pd or PdO phases different dependencies of surface and bulk characteristics. For
emerged when using unary, ternary, or quaternary fluorite oxides as HEAs, the reactants, intermediates, and products are confined on
substrate, validating the entropy-induced behavior. Employment the metal surfaces. The energetic barrier for metal constituents to
of fumed silica as templates realized the construction of the porous migrate is high, which is further restrained by the sluggish diffusion
Pd1@HEFO structure, exposing an appreciable amount of isolated kinetics of HEAs. In contrast, the mobile oxygen species both on the
Pd atoms on the oxide surface. Catalytic measurements reflected surface and in bulk of metal oxides contribute to the catalytic per-
improved surface reducibility, and enriched oxygen vacancies pro- formances, which have been proven for electrocatalytic OER and
mote adsorption and activation of molecular oxygen, encompassing thermocatalytic methane oxidation (128, 129). Therefore, tailoring
enhanced CO oxidation activities. The Pd1@HEFO catalyst also the creation, transformation, and migration of the activated oxygen
exhibited outstanding thermal and hydrothermal stabilities for the species on the surface and in bulk of HEOs is of vital importance to
simultaneous oxidation of CO, C3H6, and NO, indicating its potential optimize the associated catalytic capabilities.
for exhaust treatment of diesel engines.
To explicate the impact of the entropic effects in modifying the
metal-support interactions, Dai and co-workers (126) investigated NOVEL HIGH-ENTROPY SYSTEMS FOR CATALYSIS
the dynamic behaviors of the HEO-supported noble metal species. Novel entropy-stabilized systems including high-entropy fluorides,
Au, which is notorious for its strong tendency toward migration nitrides, sulfides, phosphides, and inorganic-organic hybrids have
and aggregation at high temperatures, was selected. Au (1 wt %) was also been designed and tailored for catalytic applications (Table 3).
stoichiometrically added to the equimolar mixture of MgO, CoO, Compared with the oxygen atoms in HEOs, the greater orbital
NiO, CuO, and ZnO and then annealed at 900°C. Interestingly, Au extension and energetic match of the p-orbitals in the nitrogen,
became well dispersed as cationic species along the formation of the phosphorous, and sulfur atoms with the d-orbitals of the metals
rock salt single-HEO phase. Control experiments with lower an- introduce additional space for tuning the electronic structures (130).
nealing temperature (700°C) or fewer types of metal oxides (NiMgOx The identified structure-property relationships will also provide
and NiMgZnOx) lead to the emergence of the separated Au phase, feedback and supplement to the established knowledge system of
indicating that this unexpected dispersion of Au into the HEO lat- HEMs, which helps understand topics such as charge redistribution
tice originated from the pronounced entropic contributions. Interest- and vacancy mediation.
ingly, a reversible behavior was observed for the Au-HEO sample. Owing to the high electronegativity, fluorine has been consid-
Au remains well dispersed within the HEO lattice at 900°C with ered as an important dopant to modify the adsorption energy of the
enlarged configurational entropy, while it precipitates out on the OER intermediates. The ABF3-type perovskite fluorides have maxi-
oxide surface at 700°C when enthalpy effect takes control (Fig. 4G). mized metal-fluorine bonds with strong ionicity and intrinsic three-
The reversible dispersion and precipitation of the Au species into dimensional diffusion channels that favor oxygen transport. However,
and out of the HEO support at different temperatures were correlated the low electrical conductivity hinders their application as efficient OER
to distinct catalytic performances, as more exposed Au sites along catalysts. Dai and colleagues (38) overcame this issue by introducing
the precipitation resulted in better CO oxidation activities. This multiple cations to the B site to produce HEPFs. Single-phase potassium-
study probes the dynamic interplay between the noble metal catalysts based HEPFs, including K(MgMnFeCoNi)F3, K(MgMnCoNiZn)F3,

K-(MnFeCoNiZn)F3, and K(MgCoNiCuZn)F3, were prepared by of molecular species. HE-ZIFs were applied for the cycloaddition of
combining hydrothermal synthesis with ball milling. This com- CO2 with epoxides to produce carbonates, which are routinely used
bined synthetic strategy can be further extended to the preparation in electrochemical and pharmaceutical industries. As shown in
of the corresponding sodium-based as well as potassium- and sodium- Fig. 5D, the five highly dispersed metal sites in the HE-ZIF function
mixed HEPFs. The optimized electrocatalyst, K0.8Na0.2(MgMnFeCoNi)F3, as efficient Lewis acidic sites in epoxide activation, giving rise to a
showed the highest alkaline OER activity, superior to that of the higher yield for the conversion of CO2 compared with that of the
individual fluorite perovskite and the commercial IrO2 catalyst. The single-cation ZIF and their physical mixtures. High-entropy metal-
enhanced electrical conductivity and mass transfer, together with organic frameworks (HE-MOFs) with a two-dimensional flower-like
the dispersed and isolated B sites, collectively contribute to the ex- morphology and good aqueous solubilities were also prepared as
cellent OER performance of K0.8Na0.2(MgMnFeCoNi)F3 (Fig. 5A). enhanced OER catalysts (Fig. 5E) (135).
The as-formed metal oxide or oxyhydroxide layers on the surface of
the HEPFs play a decisive role in accelerating the sluggish proton-
coupled electron transfer process. HEO-fluoride solid solutions were MOVING FORWARD: OPPORTUNITIES AND CHALLENGES
also prepared via mechanical synthesis, where independent compo- Despite rapid developments in the synthesis, characterization, and
sitional tuning at both anionic and cationic sites enables outstanding catalytic applications of HEMs, only a small part of the wide com-
OER performances (131). positional space has been explored. Most studies have been driven
More crystalline high-entropy compounds with advantageous by the notion that HEMs could deliver better performances as an

electrochemical properties have been fabricated and interrogated. extension to conventional alloys. This has somewhat limited the
As illustrated in Fig. 5B, Dai and colleagues (132) prepared high- catalytic applications of HEMs, since there is a much broader area
entropy metal nitrides using a soft urea strategy assisted by mechano- involving more catalytic conversions awaiting to be investigated.
chemical synthesis. Five equimolar metals including V, Cr, Nb, Mo, and HEMs have also exhibited great potential to fundamentally tackle
Zr homogeneously distribute in the single-phase cubic nitride lattice. issues that are considered challenging for unary and traditional
Hu and colleagues (39) prepared high-entropy metal sulfide nanopar- multicomponent systems. This paradigm shift from “using materials
ticles by modifying the carbothermal shock technique. The ultrafast that we have” to “engineering materials that we need” (76) could be
thermal pulse process facilitated the reaction between the metal atoms a game-changing opportunity for both materials and catalysis com-
and sulfur, producing single-phase cubic-structured (CrMnFeCoNi)Sx munities to embrace. Here, we briefly outline the upcoming oppor-
nanoparticles. The OER performance of (CrMnFeCoNi)Sx exceeded tunities and challenges in this interdisciplinary field (Fig. 6A).
that of the unary, binary, ternary, and quaternary sulfide counter-
parts (Fig. 5C), which was ascribed to the effective modulation of the Synthesis and characterization
electronic structure. The improved electrochemical performance was Controllable synthesis and precise characterization are the corner-
also demonstrated for high-entropy metal phosphides, which contain stones for the discovery and design of HEM-based catalysts. The
equimolar Co, Cr, Fe, Mn, and Ni in a hexagonal structure (133). aims will be twofold from a materials perspective. The first is to in-
Because of the limited high-temperature stabilities of molecular crease the synthetic accessibility of HEMs, which is currently limited
linkers, the preparation of high-entropy inorganic-organic hybrids by the use of special instruments and exquisite tuning of the syn-
is considered synthetically challenging. Dai and co-workers (134) thetic parameters. While entropy-stabilized systems are thermody-
turned to mechanochemistry and successfully fabricated high- namically favorable at elevated temperatures, studies have indicated
entropy zeolitic imidazolate frameworks (HE-ZIFs) under ambient that it is possible to access various nanostructured HEMs at lower
conditions. During the ball milling process, the local short-range heat- temperatures. Ball milling has been regarded as a revolutionary route
ing accelerates molecular diffusion, resulting in a random dispersion to realizing atomic mixing of the ionic and molecular precursors
of Zn2+, Co2+, Cd2+, Ni2+, and Cu2+ in the ZIF lattice coordinated by under solvent-free or minimal-solvent conditions (136). Solvothermal
the 2-methylimidazole linker. With the three-dimensional frame- synthesis, which induces an autocatalytic formation pathway of HEA
works that are isomorphous with zeolites, the HE-ZIF maintained a nanoparticles, has also been demonstrated (32). Meanwhile, revisiting
high surface area (1147 m2 g−1) that is beneficial to the adsorption some of the entropy processes could bring additional inspirations
Table 3. Summary of novel HEMs for thermocatalysis and electrocatalysis. T, thermocatalysis; E, electrocatalysis.
Ball milling + solvothermal
KNa(MgMnFeCoNi)F3 Perovskite OER (E) (38)
synthesis
[La(CrMnFeCoNi)O3]3/4
Perovskite Ball milling OER (E) (131)
[K(MgMnFeCoNi)F3]1/4
CrMnFeCoNiSx Mainly cubic Carbothermal shock OER (E) (39)
CoCrFeMnNiPx Hexagonal Eutectic synthesis OER (E) and HER (E) (133)
Cycloaddition of CO2 with
ZnCoCdNiCu/MIM ZIF Ball milling (134)
epoxides (T)
Ambient solution-phase
MnFeCoNiCu/BDC MOF OER (E) (135)
method


Fig. 5. New high-entropy systems for catalysis. (A) Comparison of the electrochemical resistance of the individual perovskite fluorides and the HEPFs. Reproduced with
permission from the American Chemical Society (38). (B) Schematic showing the synthetic pathway toward high-entropy metal nitrides, combining the soft urea strategy
with mechanochemistry. Reproduced with permission from John Wiley and Sons (132). (C) Comparison of the OER overpotentials and metal element numbers among
unary, binary, ternary, and quaternary sulfides and quinary (CrMnFeCoNi)Sx high-entropy metal sulfides. Reproduced with permission from John Wiley and Sons (39).
(D) Yield comparison of cyclic carbonates from CO2 cycloaddition with epoxides catalyzed by the HE-ZIF-BM, single-metal ZIFs (ZIF-8-BM, Cd-ZIF-8, and ZIF-67), and physical
mixture of the three single-metal ZIFs (PM-ZIF), respectively. Reproduced with permission from John Wiley and Sons (134). (E) TEM image of the HE-MOF nanosheets and
the Tyndall effect highlighted in the inset display good aqueous dispersibility. Reproduced with permission from the Royal Society of Chemistry (135).
for synthesis. For instance, cation exchange in colloidal nanocrystals is delicate tuning of the steric and electronic properties that are desir-
a process determined by enthalpic and entropic factors involving hard- able for catalytic applications. Advanced characterization techniques,
soft acid-base interactions between metal cationic species and molecular such as atom probe tomography demonstrated by Yaghi and col-
ligands (137). Inspired by this, Schaak and co-workers (33) recently leagues (140) (Fig. 6C), will enable identification of the atomic con-
introduced multication exchange as a low-temperature pathway to col- figurations in both hard and soft HEMs. This is also useful to bridge
loidal high-entropy sulfide nanoparticles (Zn0.25Co0.22Cu0.28In0.16Ga0.11S). A the gap between surface atom sequence and corresponding adsorp-
continuous-flow reactor was also developed by Kusada et al. (138), tion behaviors of molecular species. Operando microscopic and
which enables the nonequilibrium, scalable flow synthesis of the spectroscopic techniques will monitor the dynamic change on the
IrPdPtRhRu HEA nanoparticles with immiscible elemental combina- surface of HEMs under various reaction conditions. While studies
tions. The proven repeatability and unprecedented producibility have primarily focused on single-phase HEMs with maximized con-
could satisfy the requirement of large-scale chemical infrastructures. figurational entropy, a wider scope of multicomponent systems con-
Further development of feasible, reliable, and scalable synthetic ap- taining multiple phases should be evaluated. Engineering the
proaches could make HEMs more accessible for catalytic discussions interface between the segregated phase and the high-entropy domain
that cover both fundamental and application-driven studies. or the one connecting different high-entropy domains in hetero-
The second target is precise control of the size and structure of structured nanoparticles (Fig. 6D) may improve the activity and
HEMs. Tailored synthetic protocols coupled with state-of-the-art selectivity of tandem catalysts, where balancing surface and inter-
characterization tools will bring atomic insights into the formation face energies becomes critical (141).
and configuration of HEMs. As illustrated in Fig. 6B, Tsukamoto et al.
(139) reported the template synthesis of multimetallic subnanoclus- Theoretical investigation
ters. The demonstrated atom hybridization provides an atomically Theoretical efforts that afford complementary insights into experimen-
resolved platform to probe interactions among different atoms and tation and accurate predictions will be of ever-increasing importance.

Fig. 6. Outlook for future studies of HEMs for catalysis. (A) Schematic showing future opportunities and challenges in HEMs for catalysis. Advanced synthetic, charac-
terization, and computational techniques will enable further exploration of the enthalpy-entropy correlation in HEMs. (B) Schematic showing the stepwise accumulation
of the metal cations on the phenylazomethine dendrimer to prepare the atomically precise Ga1In1Au3Bi2Sn6. Reproduced with permission from the Nature Publishing
Group (http://creativecommons.org/licenses/by/4.0/) (139). (C) Schematic showing the use of atom probe tomography to map the metal sequence in the multivariate
MOF samples. Reproduced with permission from the American Association for the Advancement of Science (140). (D) High-resolution TEM image of the junction in an
Au─Co─PdSn nanoparticle (scale bar, 3 nm), where the insets show the ADF-STEM image and corresponding EDS element map of the entire nanoparticle. The FFT pat-
terns corresponding to the Au, Co, and PdSn domains are put at the bottom, and the three phase boundaries are highlighted with dashed lines. Reproduced with permis-
sion from the American Association for the Advancement of Science (141). (E) Ionic conductivities of the Li- and Na-doped MgCoNiCuZnOx HEOs at 20° and 80°C, which
are notably improved compared with that of the nitrogen doped lithium phosphate glass (LIPON) solid electrolyte. Reproduced with permission from the Royal Society
of Chemistry (146). (F) Structure evolution of the CoCrFeMnNi HEA as monitored by the XRD patterns, corresponding to the transition between the initial fcc lattice and the
pressured-induced hcp structure. Reproduced with permission from the Nature Publishing Group (http://creativecommons.org/licenses/by/4.0/) (148). (G) Faradic
efficiencies of the Cu1–xAgx bimetallics with different compositions for electrochemical CO reduction at −0.70 ± 0.01 V versus RHE. Reproduced with permission from the
American Association for the Advancement of Science (http://creativecommons.org/licenses/by-nc/4.0/legalcode) (149).

Topics such as formation and stabilization of the high- and medium- activated to facilitate movement of the oxygen ions (147). Ideally,
entropy phases, interaction between the intermediate absorbates the binding enthalpy (Ha) reaches a minimal value that corre-
and the HEM surface, and high-throughput screening of potential sponds to the maximum of the conductivity. For thermal catalysis,
chemical combinations all require inputs using computational tools. this nonclassical feature of HEOs can be used to improve the
The well-established catalysis theory can hardly be extended to oxygen transport for high-temperature oxidation reactions. Entropy-
entropy-stabilized regimes owing to the unprecedented structural and induced reduction of the energetic barrier for lattice oxygen acti-
compositional complexities. For example, in the case of the HEA vation may endow HEOs as compelling catalyst supports. This is
electrocatalysts for ORR, the scaling relationship between the *OH particularly useful for high-temperature reactions that rely on the
and *OOH intermediates is conserved for the adsorption on the intrafacial mechanism, where the inferior oxygen transport limits
HEA surface, because they both bind at an on-top position. The migration of the active oxygen species from the interior bulk lattice
scaling relation between *OH and *O, on the other hand, is no longer to the surface active sites (129).
valid since they tend to bind in different manners (13). Therefore, Polymorphism, which has been demonstrated for the high-
additional parameters may be needed for theoretical discussions entropy Cantor alloy (CoCrFeMnNi) (148), will be another intrigu-
on HEMs for catalysis. ing subject (Fig. 6F). The ability to realize atomic-level control of
Machine learning has received a lot of attention because of its composition and configuration of HEMs has only been achieved
unparalleled capability to multiprocess data and automatically build with computational tools (73). Comparisons among different HEM
analytical models to identify the optimal composition and structure catalysts with different structures but identical elemental composi-

of HEMs. However, it still requires designation of descriptors to en- tion and microstructure will help unveil the atomic arrangement
able assessment of the data points (142). Three common descriptors that underpins the surface adsorption properties. Benchmarking
are geometric parameters that are determined by the atomic posi- the performance of HEMs with related systems is also important.
tions, electronic factors describing electronic structures, and ener- This has been lacking due to the various forms of HEMs including
getic features involving adsorption energies of molecular species bulk powders, thin films, nanoporous architectures, supported
and formation energies of certain structures. Therefore, coordinat- nanoparticles, and difficulty in identifying and quantifying the cat-
ing the use of these three descriptors and developing reliable machine alytic active sites for different reactions. Proper control with unified
learning models with decreased dependency on the DFT-calculated standards and reporting metrics will allow accurate attribution of
values are desired. In addition, different algorithms should be the catalytic properties to the key features of HEMs.
adopted for different purposes (143). For example, convolutional Continuous composition tuning in a controlled manner is at-
neural networks allow accurate and efficient prediction of electronic tractive for catalysis, as strong cooperative effects among different
properties. In contrast, graph neural networks with more flexible metals could bring synergistic properties that are inaccessible with
inputs work better to probe the atomic structures involving atom the individual constituent. However, this has been greatly ham-
and bonding information. pered by the large miscibility gap in the bulk phases. Recent advanc-
It is also important to analyze the deviation between experimental es in HEAs have indicated that tunable amounts of certain metals
data and computational results, which will unveil additional parameters can be incorporated to the single entropy-stabilized phase. This af-
to include to achieve more accurate predictions. The stability debate fords a powerful route to overcoming the miscibility limitation and
on the HEA catalysts is a good example. Previous theoretical realizing the full potential of entropic stabilizations (67). Moreover,
work indicated the structure of HEAs is thermodynamically stable, the gained knowledge between thermodynamic and kinetic factors
which can be ascribed to the sluggish diffusion kinetics (73, 74). How- can be extended to simple systems. For example, Hu and colleagues
ever, surface structuring, restructuring, and phase segregation have (149) overcame the inherent immiscibility in Cu-based bimetallic
been experimentally observed (77). This deviation could be resulted systems by using the carbothermal shock technique, which was first
by the difference in the practical and simulated environment. Tem- developed to prepare nanostructured HEAs. Cu0.9Ni0.1 and Cu0.9Ag0.1
perature difference could be a common cause, especially for DFT exhibited enhanced capabilities for the electrochemical reduction of
calculations. Monte Carlo methods have been used to help assess the CO2 compared with that of pure Cu (Fig. 6G). Understanding and
stability of HEAs at high temperatures (37, 64). Besides, vacuum is tailoring the nonequilibrium synthetic process will introduce access
typically adopted for calculations, whereas the gas- and solution- to the restricted area in traditional alloy systems.
phase environments in practice are much more complex. Adsorbate-
induced surface segregation, which has been widely studied for
monometallic and alloy nanoparticles but not for HEAs (144, 145), SUMMARY AND OUTLOOK
can be an informative starting point to connect the experimental HEMs have emerged as a versatile family of materials exhibiting in-
and computational results. triguing catalytic properties. Here, we summarize recent advances
in applying HEAs, HEOs, and beyond for catalytic applications. As
Probing the enthalpy-entropy correlation for catalysis the prototype of HEMs, HEAs provide diverse surface metal sites
Another fundamental goal is to articulate the enthalpy-entropy cor- with highly tunable adsorption energies for reaction intermediates.
relation in HEMs and discover new properties or extrapolate defined Studies on HEOs as catalysts and catalyst supports demonstrate the
features that have been applied for other applications to catalysis. For feasibility of adjusting the oxygen part via controlling the configu-
instance, the prototypical rock salt HEOs (Co0.2Ni0.2Cu0.2Mg0.2Zn0.2O) rational entropy. Besides hard materials, soft inorganic-organic hy-
exhibited superior ionic (Li+ and Na+) mobilities (Fig. 6E), which brids have also been studied to fine-tune the Lewis acidic sites in a
was attributed to the promotion of oxygen vacancies in the highly controlled manner. While these studies have unambiguously proven
disordered structures (146). In oxide-ion conductors, the defect the significance of regulating the configurational entropy on the catalyst
pairs between the dopant cation and the oxygen vacancy need to be side, more work is anticipated to further interpret the correlation

between structural and compositional engineering and optimiza- 26. A. Khorshidi, J. Violet, J. Hashemi, A. A. Peterson, How strain can break the scaling
tion of the catalytic behaviors. Advanced synthetic, computational, relations of catalysis. Nat. Catal. 1, 263–268 (2018).
27. K.-Y. Tsai, M.-H. Tsai, J.-W. Yeh, Sluggish diffusion in Co–Cr–Fe–Mn–Ni high-entropy
and characterization approaches will give rise to an expanded and
alloys. Acta Mater. 61, 4887–4897 (2013).
well-defined library of HEMs, with predictive tuning of the lattice, 28. D. B. Miracle, O. N. Senkov, A critical review of high entropy alloys and related concepts.
occupancy, surface, interface, defect, etc. Meanwhile, interactions Acta Mater. 122, 448–511 (2017).
between the reactants, intermediates, and products, and the catalytic 29. Y. Yao, Z. Huang, P. Xie, S. D. Lacey, R. J. Jacob, H. Xie, F. Chen, A. Nie, T. Pu, M. Rehwoldt,
platform with manageable entropic contributions will bring useful D. Yu, M. R. Zachariah, C. Wang, R. Shahbazian-Yassar, J. Li, L. Hu, Carbothermal shock
synthesis of high-entropy-alloy nanoparticles. Science 359, 1489–1494 (2018).
insights into efficient and selective catalytic reactions. These cohe- 30. S. Gao, S. Hao, Z. Huang, Y. Yuan, S. Han, L. Lei, X. Zhang, R. Shahbazian-Yassar, J. Lu,
sive efforts will tie the catalysis and materials communities, intro- Synthesis of high-entropy alloy nanoparticles on supports by the fast moving bed
ducing a new frontier for the discovery and design of efficient pyrolysis. Nat. Commun. 11, 2016 (2020).
catalytic materials. 31. H. Xu, Z. Zhang, J. Liu, C.-L. Do-Thanh, H. Chen, S. Xu, Q. Lin, Y. Jiao, J. Wang, Y. Wang,
Y. Chen, S. Dai, Entropy-stabilized single-atom Pd catalysts via high-entropy fluorite
oxide supports. Nat. Commun. 11, 3908 (2020).
REFERENCES AND NOTES 32. N. L. N. Broge, M. Bondesgaard, F. Søndergaard-Pedersen, M. Roelsgaard, B. B. Iversen,
1. M. I. Page, Entropy, binding energy, and enzymic catalysis. Angew. Chem. Int. Ed. 16, Autocatalytic formation of high-entropy alloy nanoparticles. Angew. Chem. Int. Ed. 59,
449–459 (1977). 21920–21924 (2020).
2. J. Åqvist, M. Kazemi, G. V. Isaksen, B. O. Brandsdal, Entropy and enzyme catalysis. 33. C. R. McCormick, R. E. Schaak, Simultaneous multication exchange pathway to high-
Acc. Chem. Res. 50, 199–207 (2017). entropy metal sulfide nanoparticles. J. Am. Chem. Soc. 143, 1017–1023 (2021).

3. R. Gounder, E. Iglesia, The roles of entropy and enthalpy in stabilizing ion-pairs at 34. D. Wu, K. Kusada, T. Yamamoto, T. Toriyama, S. Matsumura, S. Kawaguchi, Y. Kubota,
transition states in zeolite acid catalysis. Acc. Chem. Res. 45, 229–238 (2012). H. Kitagawa, Platinum-group-metal high-entropy-alloy nanoparticles. J. Am. Chem. Soc.
4. J. F. M. Denayer, R. A. Ocakoglu, I. C. Arik, C. E. A. Kirschhock, J. A. Martens, G. V. Baron, 142, 13833–13838 (2020).
Rotational entropy driven separation of alkane/isoalkane mixtures in zeolite cages.
35. Y. Sun, A. J. Darling, Y. Li, K. Fujisawa, C. F. Holder, H. Liu, M. J. Janik, M. Terrones,
Angew. Chem. Int. Ed. 44, 400–403 (2005).
R. E. Schaak, Defect-mediated selective hydrogenation of nitroarenes on nanostructured
5. C. T. Campbell, The energetics of supported metal nanoparticles: Relationships
WS2. Chem. Sci. 10, 10310–10317 (2019).
to sintering rates and catalytic activity. Acc. Chem. Res. 46, 1712–1719 (2013).
36. G. Liu, A. W. Robertson, M. M.-J. Li, W. C. H. Kuo, M. T. Darby, M. H. Muhieddine, Y.-C. Lin,
6. M. E. Strayer, T. P. Senftle, J. P. Winterstein, N. M. Vargas-Barbosa, R. Sharma, R. M. Rioux,
K. Suenaga, M. Stamatakis, J. H. Warner, S. C. E. Tsang, MoS2 monolayer catalyst doped
M. J. Janik, T. E. Mallouk, Charge transfer stabilization of late transition metal oxide
with isolated Co atoms for the hydrodeoxygenation reaction. Nat. Chem. 9, 810–816 (2017).
nanoparticles on a layered niobate support. J. Am. Chem. Soc. 137, 16216–16224 (2015).
37. T. Li, Y. Yao, Z. Huang, P. Xie, Z. Liu, M. Yang, J. Gao, K. Zeng, A. H. Brozena, G. Pastel,
7. G. Zhu, Z. Huang, Z. Xu, L. T. Yan, Tailoring interfacial nanoparticle organization through
M. Jiao, Q. Dong, J. Dai, S. Li, H. Zong, M. Chi, J. Luo, Y. Mo, G. Wang, C. Wang,
entropy. Acc. Chem. Res. 51, 900–909 (2018).
R. Shahbazian-Yassar, L. Hu, Denary oxide nanoparticles as highly stable catalysts
8. D. Feng, Y. Dong, L. Zhang, X. Ge, W. Zhang, S. Dai, Z. Qiao, Holey lamellar high-entropy
for methane combustion. Nat. Catal. 4, 62–70 (2021).
oxide as an ultra-high-activity heterogeneous catalyst for solvent-free aerobic oxidation
38. T. Wang, H. Chen, Z. Yang, J. Liang, S. Dai, High-entropy perovskite fluorides: A new
of benzyl alcohol. Angew. Chem. Int. Ed. 59, 19503–19509 (2020).
platform for oxygen evolution catalysis. J. Am. Chem. Soc. 142, 4550–4554 (2020).
9. Y. Shu, J. Bao, S. Yang, X. Duan, P. Zhang, Entropy-stabilized metal-CeOx solid solutions
39. M. Cui, C. Yang, B. Li, Q. Dong, M. Wu, S. Hwang, H. Xie, X. Wang, G. Wang, L. Hu,
for catalytic combustion of volatile organic compounds. AICHE J. 67, e17046 (2021).
High-entropy metal sulfide nanoparticles promise high-performance oxygen evolution
10. Y. Xin, S. Li, Y. Qian, W. Zhu, H. Yuan, P. Jiang, R. Guo, L. Wang, High-entropy alloys
reaction. Adv. Energy Mater. 11, 2002887 (2021).
as a platform for catalysis: Progress, challenges, and opportunities. ACS Catal. 10,
40. C. F. Holder, R. E. Schaak, Tutorial on powder x-ray diffraction for characterizing nanoscale
11280–11306 (2020).
materials. ACS Nano 13, 7359–7365 (2019).
11. T. Löffler, A. Savan, A. Garzón-Manjón, M. Meischein, C. Scheu, A. Ludwig, W. Schuhmann,
Toward a paradigm shift in electrocatalysis using complex solid solution nanoparticles. 41. B. Jiang, C. A. Bridges, R. R. Unocic, K. C. Pitike, V. R. Cooper, Y. Zhang, D.-Y. Lin, K. Page,
ACS Energy Lett. 4, 1206–1214 (2019). Probing the local site disorder and distortion in pyrochlore high-entropy oxides. J. Am.
12. H. Zheng, G. Luo, A. Zhang, X. Lu, L. He, The synthesis and catalytic applications Chem. Soc. 143, 4193–4204 (2021).
of nanosized high-entropy alloys. ChemCatChem 13, 806–817 (2021). 42. Y. Ren, X. Zuo, Synchrotron x-ray and neutron diffraction, total scattering, and small-angle
13. J. K. Pedersen, T. A. A. Batchelor, D. Yan, L. E. J. Skjegstad, J. Rossmeisl, Surface scattering techniques for rechargeable battery research. Small Methods 2, 1800064 (2018).
electrocatalysis on high-entropy alloys. Curr. Opin. Electrochem. 26, 100651 (2021). 43. L. J. Santodonato, Y. Zhang, M. Feygenson, C. M. Parish, M. C. Gao, R. J. K. Weber,
14. G. M. Tomboc, T. Kwon, J. Joo, K. Lee, High entropy alloy electrocatalysts: A critical J. C. Neuefeind, Z. Tang, P. K. Liaw, Deviation from high-entropy configurations in the atomic
assessment of fabrication and performance. J. Mater. Chem. A 8, 14844–14862 (2020). distributions of a multi-principal-element alloy. Nat. Commun. 6, 5964 (2015).
15. K. Li, W. Chen, Recent progress in high-entropy alloys for catalysts: Synthesis, 44. Z. Saghi, P. A. Midgley, Electron tomography in the (S)TEM: From nanoscale
applications, and prospects. Mater. Today Energy. 20, 100638 (2021). morphological analysis to 3D atomic imaging. Annu. Rev. Mater. Res. 42, 59–79 (2012).
16. H. Li, H. Zhu, S. Zhang, N. Zhang, M. Du, Y. Chai, Nano high-entropy materials: Synthesis 45. Q. Ding, Y. Zhang, X. Chen, X. Fu, D. Chen, S. Chen, L. Gu, F. Wei, H. Bei, Y. Gao, M. Wen,
strategies and catalytic applications. Small Struct. 1, 2000033 (2020). J. Li, Z. Zhang, T. Zhu, R. O. Ritchie, Q. Yu, Tuning element distribution, structure
17. T. Montini, M. Melchionna, M. Monai, P. Fornasiero, Fundamentals and catalytic and properties by composition in high-entropy alloys. Nature 574, 223–227 (2019).
applications of CeO2-based materials. Chem. Rev. 116, 5987–6041 (2016). 46. H. von Harrach, D. Klenov, B. Freitag, P. Schlossmacher, P. Collins, H. Fraser, Comparison
18. D. Kim, C. Xie, N. Becknell, Y. Yu, M. Karamad, K. Chan, E. J. Crumlin, J. K. Nørskov, P. Yang, of the detection limits of EDS and EELS in S/TEM. Microsc. Microanal. 16, 1312–1313 (2010).
Electrochemical activation of CO2 through atomic ordering transformations of AuCu 47. P. L. Gai, E. D. Boyes, S. Helveg, P. L. Hansen, S. Giorgio, C. R. Henry, Atomic-resolution
nanoparticles. J. Am. Chem. Soc. 139, 8329–8336 (2017). environmental transmission electron microscopy for probing gas–solid reactions
19. X. Chang, M. Zeng, K. Liu, L. Fu, Phase engineering of high-entropy alloys. Adv. Mater. 32, in heterogeneous catalysis. MRS Bull. 32, 1044–1050 (2007).
1907226 (2020). 48. M. Fracchia, P. Ghigna, T. Pozzi, U. Anselmi Tamburini, V. Colombo, L. Braglia, P. Torelli,
20. E. P. George, D. Raabe, R. O. Ritchie, High-entropy alloys. Nat. Rev. Mater. 4, 515–534 (2019). Stabilization by configurational entropy of the Cu(II) active site during CO oxidation
21. J.-W. Yeh, S.-K. Chen, S.-J. Lin, J.-Y. Gan, T.-S. Chin, T.-T. Shun, C.-H. Tsau, S.-Y. Chang, on Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O. J. Phys. Chem. Lett. 11, 3589–3593 (2020).
Nanostructured high-entropy alloys with multiple principal elements: Novel alloy design 49. Y. Sun, Y. Wang, J. Y. C. Chen, K. Fujisawa, C. F. Holder, J. T. Miller, V. H. Crespi, M. Terrones,
concepts and outcomes. Adv. Eng. Mater. 6, 299–303 (2004). R. E. Schaak, Interface-mediated noble metal deposition on transition metal
22. Y. F. Ye, Q. Wang, J. Lu, C. T. Liu, Y. Yang, High-entropy alloy: Challenges and prospects. dichalcogenide nanostructures. Nat. Chem. 12, 284–293 (2020).
Mater. Today 19, 349–362 (2016). 50. Z. W. Chen, L. X. Chen, Z. Wen, Q. Jiang, Understanding electro-catalysis by using density
23. F. Otto, Y. Yang, H. Bei, E. P. George, Relative effects of enthalpy and entropy on the phase functional theory. Phys. Chem. Chem. Phys. 21, 23782–23802 (2019).
stability of equiatomic high-entropy alloys. Acta Mater. 61, 2628–2638 (2013). 51. L. J. Santodonato, P. K. Liaw, R. R. Unocic, H. Bei, J. R. Morris, Predictive multiphase
24. B. Cantor, I. T. H. Chang, P. Knight, A. J. B. Vincent, Microstructural development evolution in Al-containing high-entropy alloys. Nat. Commun. 9, 4520 (2018).
in equiatomic multicomponent alloys. Mater. Sci. Eng. A 375–377, 213–218 (2004). 52. J. F. Callejas, C. G. Read, C. W. Roske, N. S. Lewis, R. E. Schaak, Synthesis, characterization,
25. J.-W. Yeh, Alloy design strategies and future trends in high-entropy alloys. JOM 65, and properties of metal phosphide catalysts for the hydrogen-evolution reaction.
1759–1771 (2013). Chem. Mater. 28, 6017–6044 (2016).

53. H. R. J. ter Veen, T. Kim, I. E. Wachs, H. H. Brongersma, Applications of high sensitivity-low 78. S. Li, X. Tang, H. Jia, H. Li, G. Xie, X. Liu, X. Lin, H.-J. Qiu, Nanoporous high-entropy alloys
energy ion scattering (HS-LEIS) in heterogeneous catalysis. Catal. Today 140, 197–201 with low Pt loadings for high-performance electrochemical oxygen reduction. J. Catal.
(2009). 383, 164–171 (2020).
54. Z. Li, K. G. Pradeep, Y. Deng, D. Raabe, C. C. Tasan, Metastable high-entropy dual-phase 79. H.-J. Qiu, G. Fang, Y. Wen, P. Liu, G. Xie, X. Liu, S. Sun, Nanoporous high-entropy alloys
alloys overcome the strength–ductility trade-off. Nature 534, 227–230 (2016). for highly stable and efficient catalysts. J. Mater. Chem. A 7, 6499–6506 (2019).
55. S. Wei, S. J. Kim, J. Kang, Y. Zhang, Y. Zhang, T. Furuhara, E. S. Park, C. C. Tasan, 80. T. Löffler, H. Meyer, A. Savan, P. Wilde, A. Garzón Manjón, Y.-T. Chen, E. Ventosa, C. Scheu,
Natural-mixing guided design of refractory high-entropy alloys with as-cast tensile A. Ludwig, W. Schuhmann, Discovery of a multinary noble metal-free oxygen reduction
ductility. Nat. Mater. 19, 1175–1181 (2020). catalyst. Adv. Energy Mater. 8, 1802269 (2018).
56. B. Gludovatz, A. Hohenwarter, D. Catoor, E. H. Chang, E. P. George, R. O. Ritchie, A 81. A. G. Manjón, T. Löffler, M. Meischein, H. Meyer, J. Lim, V. Strotkötter, W. Schuhmann,
fracture-resistant high-entropy alloy for cryogenic applications. Science 345, 1153–1158 A. Ludwig, C. Scheu, Sputter deposition of highly active complex solid solution
(2014). electrocatalysts into an ionic liquid library: Effect of structure and composition on oxygen
57. C. Lee, G. Kim, Y. Chou, B. L. Musicó, M. C. Gao, K. An, G. Song, Y.-C. Chou, V. Keppens, reduction activity. Nanoscale 12, 23570–23577 (2020).
W. Chen, P. K. Liaw, Temperature dependence of elastic and plastic deformation behavior 82. T. Löffler, F. Waag, B. Gökce, A. Ludwig, S. Barcikowski, W. Schuhmann, Comparing
of a refractory high-entropy alloy. Sci. Adv. 6, eaaz4748 (2020). the activity of complex solid solution electrocatalysts using inflection points
58. Z. Fu, L. Jiang, J. L. Wardini, B. E. MacDonald, H. Wen, W. Xiong, D. Zhang, Y. Zhou, of voltammetric activity curves as activity descriptors. ACS Catal. 11, 1014–1023 (2021).
T. J. Rupert, W. Chen, E. J. Lavernia, A high-entropy alloy with hierarchical 83. T. Löffler, A. Savan, H. Meyer, M. Meischein, V. Strotkötter, A. Ludwig, W. Schuhmann,
nanoprecipitates and ultrahigh strength. Sci. Adv. 4, eaat8712 (2018). Design of complex solid-solution electrocatalysts by correlating configuration,
59. A. V. Okulov, S.-H. Joo, H. S. Kim, H. Kato, I. V. Okulov, Nanoporous high-entropy alloy by adsorption energy distribution patterns, and activity curves. Angew. Chem. Int. Ed. 59,
liquid metal dealloying. Metals 10, 1396 (2020). 5844–5850 (2020).
60. S. H. Joo, J. W. Bae, W. Y. Park, Y. Shimada, T. Wada, H. S. Kim, A. Takeuchi, T. J. Konno, 84. K. Huang, B. Zhang, J. Wu, T. Zhang, D. Peng, X. Cao, Z. Zhang, Z. Li, Y. Huang, Exploring

H. Kato, I. V. Okulov, Beating thermal coarsening in nanoporous materials via the impact of atomic lattice deformation on oxygen evolution reactions based
high-entropy design. Adv. Mater. 32, 1906160 (2020). on a sub-5 nm pure face-centred cubic high-entropy alloy electrocatalyst. J. Mater.
61. X. Wang, Z. Huang, Y. Yao, H. Qiao, G. Zhong, Y. Pei, C. Zheng, D. Kline, Q. Xia, Z. Lin, J. Dai, Chem. A 8, 11938–11947 (2020).
M. R. Zachariah, B. Yang, R. Shahbazian-Yassar, L. Hu, Continuous 2000 K droplet-to- 85. X. Cui, B. Zhang, C. Zeng, S. Guo, Electrocatalytic activity of high-entropy alloys toward
particle synthesis. Mater. Today 35, 106–114 (2020). oxygen evolution reaction. MRS Commun. 8, 1230–1235 (2018).
62. Y. Yang, B. Song, X. Ke, F. Xu, K. N. Bozhilov, L. Hu, R. Shahbazian-Yassar, M. R. Zachariah, 86. F. Waag, Y. Li, A. R. Ziefuß, E. Bertin, M. Kamp, V. Duppel, G. Marzun, L. Kienle,
Aerosol synthesis of high entropy alloy nanoparticles. Langmuir 36, 1985–1992 (2020). S. Barcikowski, B. Gökce, Kinetically-controlled laser-synthesis of colloidal high-entropy
63. X. Wang, Q. Dong, H. Qiao, Z. Huang, M. T. Saray, G. Zhong, Z. Lin, M. Cui, A. Brozena, alloy nanoparticles. RSC Adv. 9, 18547–18558 (2019).
M. Hong, Q. Xia, J. Gao, G. Chen, R. Shahbazian-Yassar, D. Wang, L. Hu, Continuous 87. S. Jin, Are metal chalcogenides, nitrides, and phosphides oxygen evolution catalysts or
synthesis of hollow high-entropy nanoparticles for energy and catalysis applications. Adv. bifunctional catalysts? ACS Energy Lett. 2, 1937–1938 (2017).
Mater. 32, 2002853 (2020). 88. B. Song, Y. Yang, M. Rabbani, T. T. Yang, K. He, X. Hu, Y. Yuan, P. Ghildiyal, V. P. Dravid,
64. Y. Yao, Z. Liu, P. Xie, Z. Huang, T. Li, D. Morris, Z. Finfrock, J. Zhou, M. Jiao, J. Gao, Y. Mao, M. R. Zachariah, W. A. Saidi, Y. Liu, R. Shahbazian-Yassar, In situ oxidation studies
J. Miao, P. Zhang, R. Shahbazian-Yassar, C. Wang, G. Wang, L. Hu, Computationally aided, of high-entropy alloy nanoparticles. ACS Nano 14, 15131–15143 (2020).
entropy-driven synthesis of highly efficient and durable multi-elemental alloy catalysts. 89. Z. Ding, J. Bian, S. Shuang, X. Liu, Y. Hu, C. Sun, Y. Yang, High entropy intermetallic–oxide
Sci. Adv. 6, eaaz0510 (2020). core–shell nanostructure as superb oxygen evolution reaction catalyst. Adv. Sustain. Syst.
65. T. E. Bell, L. Torrente-Murciano, H2 production via ammonia decomposition using 4, 1900105 (2020).
non-noble metal catalysts: A review. Top. Catal. 59, 1438–1457 (2016). 90. Z. Jin, J. Lv, H. Jia, W. Liu, H. Li, Z. Chen, X. Lin, G. Xie, X. Liu, S. Sun, H. Qiu, Nanoporous
66. C. J. H. Jacobsen, S. Dahl, B. S. Clausen, S. Bahn, A. Logadottir, J. K. Nørskov, Catalyst Al-Ni-Co-Ir-Mo high-entropy alloy for record-high water splitting activity in acidic
design by interpolation in the periodic table: Bimetallic ammonia synthesis catalysts. environments. Small 15, 1904180 (2019).
J. Am. Chem. Soc. 123, 8404–8405 (2001). 91. H.-J. Qiu, G. Fang, J. Gao, Y. Wen, J. Lv, H. Li, G. Xie, X. Liu, S. Sun, Noble metal-free
67. P. Xie, Y. Yao, Z. Huang, Z. Liu, J. Zhang, T. Li, G. Wang, R. Shahbazian-Yassar, L. Hu, nanoporous high-entropy alloys as highly efficient electrocatalysts for oxygen evolution
C. Wang, Highly efficient decomposition of ammonia using high-entropy alloy catalysts. reaction. ACS Mater. Lett. 1, 526–533 (2019).
Nat. Commun. 10, 4011 (2019). 92. S. Li, J. Wang, X. Lin, G. Xie, Y. Huang, X. Liu, H. Qiu, Flexible solid-state direct ethanol fuel
68. J. Pérez-Ramírez, N. López, Strategies to break linear scaling relationships. Nat. Catal. 2, cell catalyzed by nanoporous high-entropy Al-Pd-Ni-Cu-Mo anode and spinel
971–976 (2019). (AlMnCo)3O4 cathode. Adv. Funct. Mater. 31, 2007129 (2021).
69. X. Ge, A. Sumboja, D. Wuu, T. An, B. Li, F. W. T. Goh, T. S. A. Hor, Y. Zong, Z. Liu, Oxygen 93. S. D. Lacey, Q. Dong, Z. Huang, J. Luo, H. Xie, Z. Lin, D. J. Kirsch, V. Vattipalli, C. Povinelli,
reduction in alkaline media: From mechanisms to recent advances of catalysts. ACS Catal. W. Fan, R. Shahbazian-Yassar, D. Wang, L. Hu, Stable multimetallic nanoparticles
5, 4643–4667 (2015). for oxygen electrocatalysis. Nano Lett. 19, 5149–5158 (2019).
70. Z. W. Seh, J. Kibsgaard, C. F. Dickens, I. Chorkendorff, J. K. Nørskov, T. F. Jaramillo, 94. G. Fang, J. Gao, J. Lv, H. Jia, H. Li, W. Liu, G. Xie, Z. Chen, Y. Huang, Q. Yuan, X. Liu, X. Lin,
Combining theory and experiment in electrocatalysis: Insights into materials design. S. Sun, H.-J. Qiu, Multi-component nanoporous alloy/(oxy)hydroxide for bifunctional
Science 355, eaad4998 (2017). oxygen electrocatalysis and rechargeable Zn-air batteries. Appl. Catal. B Environ. 268,
71. S. Wang, H. Xin, Predicting catalytic activity of high-entropy alloys for electrocatalysis. 118431 (2020).
Chem 5, 502–504 (2019). 95. M. Liu, Z. Zhang, F. Okejiri, S. Yang, S. Zhou, S. Dai, Entropy-maximized synthesis
72. J. K. Nørskov, J. Rossmeisl, A. Logadottir, L. Lindqvist, J. R. Kitchin, T. Bligaard, H. Jónsson, of multimetallic nanoparticle catalysts via a ultrasonication-assisted wet chemistry
Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B method under ambient conditions. Adv. Mater. Interfaces 6, 1900015 (2019).
108, 17886–17892 (2004). 96. H. Xin, A. Vojvodic, J. Voss, J. K. Nørskov, F. Abild-Pedersen, Effects of d-band shape
73. T. A. A. Batchelor, J. K. Pedersen, S. H. Winther, I. E. Castelli, K. W. Jacobsen, J. Rossmeisl, on the surface reactivity of transition-metal alloys. Phys. Rev. B 89, 115114 (2014).
High-entropy alloys as a discovery platform for electrocatalysis. Joule 3, 834–845 (2019). 97. D. Wu, K. Kusada, T. Yamamoto, T. Toriyama, S. Matsumura, I. Gueye, O. Seo, J. Kim,
74. Z. Lu, Z. W. Chen, C. V. Singh, Neural network-assisted development of high-entropy alloy S. Hiroi, O. Sakata, S. Kawaguchi, Y. Kubota, H. Kitagawa, On the electronic structure
catalysts: Decoupling ligand and coordination effects. Matter 3, 1318–1333 (2020). and hydrogen evolution reaction activity of platinum group metal-based high-entropy-
75. Y. Yao, Z. Huang, T. Li, H. Wang, Y. Liu, H. S. Stein, Y. Mao, J. Gao, M. Jiao, Q. Dong, J. Dai, alloy nanoparticles. Chem. Sci. 11, 12731–12736 (2020).
P. Xie, H. Xie, S. D. Lacey, I. Takeuchi, J. M. Gregoire, R. Jiang, C. Wang, A. D. Taylor, 98. Z. Jia, T. Yang, L. Sun, Y. Zhao, W. Li, J. Luan, F. Lyu, L. C. Zhang, J. J. Kruzic, J. J. Kai,
R. Shahbazian-Yassar, L. Hu, High-throughput, combinatorial synthesis of multimetallic J. C. Huang, J. Lu, C. T. Liu, A novel multinary intermetallic as an active electrocatalyst
nanoclusters. Proc. Natl. Acad. Sci. 117, 6316–6322 (2020). for hydrogen evolution. Adv. Mater. 32, 2000385 (2020).
76. T. A. A. Batchelor, T. Löffler, B. Xiao, O. A. Krysiak, V. Strotkötter, J. K. Pedersen, 99. R. Q. Yao, Y. T. Zhou, H. Shi, W. Bin Wan, Q. H. Zhang, L. Gu, Y. F. Zhu, Z. Wen, X. Y. Lang,
C. M. Clausen, A. Savan, Y. Li, W. Schuhmann, J. Rossmeisl, A. Ludwig, Complex-solid- Q. Jiang, Nanoporous surface high-entropy alloys as highly efficient multisite
solution electrocatalyst discovery by computational prediction and high-throughput electrocatalysts for nonacidic hydrogen evolution reaction. Adv. Funct. Mater. 31,
experimentation. Angew. Chem. Int. Ed. 60, 6932–6937 (2021). 2009613 (2021).
77. Y. Chen, X. Zhan, S. L. A. Bueno, I. H. Shafei, H. M. Ashberry, K. Chatterjee, L. Xu, Y. Tang, 100. M. W. Glasscott, A. D. Pendergast, S. Goines, A. R. Bishop, A. T. Hoang, C. Renault, J. E. Dick,
S. E. Skrabalak, Synthesis of monodisperse high entropy alloy nanocatalysts from core@ Electrosynthesis of high-entropy metallic glass nanoparticles for designer, multi-
shell nanoparticles. Nanoscale Horiz. 6, 231–237 (2021). functional electrocatalysis. Nat. Commun. 10, 2650 (2019).

101. M. Jouny, J.-J. Lv, T. Cheng, B. H. Ko, J.-J. Zhu, W. A. Goddard, F. Jiao, Formation of carbon– 128. A. Grimaud, O. Diaz-Morales, B. Han, W. T. Hong, Y. L. Lee, L. Giordano, K. A. Stoerzinger,
nitrogen bonds in carbon monoxide electrolysis. Nat. Chem. 11, 846–851 (2019). M. T. M. Koper, Y. Shao-Horn, Activating lattice oxygen redox reactions in metal oxides
102. J. K. Pedersen, T. A. A. Batchelor, A. Bagger, J. Rossmeisl, High-entropy alloys as catalysts to catalyse oxygen evolution. Nat. Chem. 9, 457–465 (2017).
for the CO2 and CO reduction reactions. ACS Catal. 10, 2169–2176 (2020). 129. J. Chen, H. Arandiyan, X. Gao, J. Li, Recent advances in catalysts for methane combustion.
103. S. Nellaiappan, N. K. Katiyar, R. Kumar, A. Parui, K. D. Malviya, K. G. Pradeep, A. K. Singh, Catal. Surv. Asia 19, 140–171 (2015).
S. Sharma, C. S. Tiwary, K. Biswas, High-entropy alloys as catalysts for the CO2 and CO 130. R. M. Bullock, J. G. Chen, L. Gagliardi, P. J. Chirik, O. K. Farha, C. H. Hendon, C. W. Jones,
reduction reactions: Experimental realization. ACS Catal. 10, 3658–3663 (2020). J. A. Keith, J. Klosin, S. D. Minteer, R. H. Morris, A. T. Radosevich, T. B. Rauchfuss,
104. C. Bianchini, P. K. Shen, Palladium-based electrocatalysts for alcohol oxidation in half cells N. A. Strotman, A. Vojvodic, T. R. Ward, J. Y. Yang, Y. Surendranath, Using nature’s
and in direct alcohol fuel cells. Chem. Rev. 109, 4183–4206 (2009). blueprint to expand catalysis with Earth-abundant metals. Science 369, eabc3183 (2020).
105. J. Feng, D. Chen, P. V. Pikhitsa, Y.-H. Jung, J. Yang, M. Choi, Unconventional alloys 131. T. Wang, J. Fan, C.-L. Do-Thanh, X. Suo, Z. Yang, H. Chen, Y. Yuan, H. Lyu, S. Yang, S. Dai,
confined in nanoparticles: Building blocks for new matter. Matter 3, 1646–1663 (2020). Perovskite oxide–halide solid solutions: A platform for electrocatalysts. Angew. Chem. Int. Ed.
106. H. Li, Y. Han, H. Zhao, W. Qi, D. Zhang, Y. Yu, W. Cai, S. Li, J. Lai, B. Huang, L. Wang, Fast 10.1002/anie.202101120, (2021).
site-to-site electron transfer of high-entropy alloy nanocatalyst driving redox 132. T. Jin, X. Sang, R. R. Unocic, R. T. Kinch, X. Liu, J. Hu, H. Liu, S. Dai, Mechanochemical-assisted
electrocatalysis. Nat. Commun. 11, 5437 (2020). synthesis of high-entropy metal nitride via a soft urea strategy. Adv. Mater. 30, 1707512 (2018).
107. D. Zhang, Y. Shi, H. Zhao, W. Qi, X. Chen, T. Zhan, S. Li, B. Yang, M. Sun, J. Lai, B. Huang, 133. X. Zhao, Z. Xue, W. Chen, Y. Wang, T. Mu, Eutectic synthesis of high-entropy metal
L. Wang, The facile oil-phase synthesis of a multi-site synergistic high-entropy alloy phosphides for electrocatalytic water splitting. ChemSusChem 13, 2038–2042 (2020).
to promote the alkaline hydrogen evolution reaction. J. Mater. Chem. A 9, 889–893 (2021). 134. W. Xu, H. Chen, K. Jie, Z. Yang, T. Li, S. Dai, Entropy-driven mechanochemical synthesis
108. D. Zhang, H. Zhao, X. Wu, Y. Deng, Z. Wang, Y. Han, H. Li, Y. Shi, X. Chen, S. Li, J. Lai, of polymetallic zeolitic imidazolate frameworks for CO2 fixation. Angew. Chem. Int. Ed. 58,
B. Huang, L. Wang, Multi-site electrocatalysts boost pH-universal nitrogen reduction by 5018–5022 (2019).
high-entropy alloys. Adv. Funct. Mater. 31, 2006939 (2021). 135. X. Zhao, Z. Xue, W. Chen, X. Bai, R. Shi, T. Mu, Ambient fast, large-scale synthesis

109. N. K. Katiyar, S. Nellaiappan, R. Kumar, K. D. Malviya, K. G. Pradeep, A. K. Singh, S. Sharma, of entropy-stabilized metal–organic framework nanosheets for electrocatalytic oxygen
C. S. Tiwary, K. Biswas, Formic acid and methanol electro-oxidation and counter hydrogen evolution. J. Mater. Chem. A 7, 26238–26242 (2019).
production using nano high entropy catalyst. Mater. Today Energy 16, 100393 (2020). 136. S. L. James, C. J. Adams, C. Bolm, D. Braga, P. Collier, T. Friščić, F. Grepioni, K. D. M. Harris,
110. C. F. Tsai, K. Y. Yeh, P. W. Wu, Y. F. Hsieh, P. Lin, Effect of platinum present in multi-element G. Hyett, W. Jones, A. Krebs, J. Mack, L. Maini, A. G. Orpen, I. P. Parkin, W. C. Shearouse,
nanoparticles on methanol oxidation. J. Alloys Compd. 478, 868–871 (2009). J. W. Steed, D. C. Waddell, Mechanochemistry: Opportunities for new and cleaner
111. C. F. Tsai, P. W. Wu, P. Lin, C. G. Chao, K. Y. Yeh, Sputter deposition of multi-element nanoparticles synthesis. Chem. Soc. Rev. 41, 413–447 (2012).
as electrocatalysts for methanol oxidation. Jpn. J. Appl. Phys. 47, 5755–5761 (2008). 137. L. De Trizio, L. Manna, Forging colloidal nanostructures via cation exchange reactions.
112. K. V. Yusenko, S. Riva, P. A. Carvalho, M. V. Yusenko, S. Arnaboldi, A. S. Sukhikh, Chem. Rev. 116, 10852–10887 (2016).
M. Hanfland, S. A. Gromilov, First hexagonal close packed high-entropy alloy 138. K. Kusada, T. Yamamoto, T. Toriyama, S. Matsumura, K. Sato, K. Nagaoka, K. Terada, Y. Ikeda,
with outstanding stability under extreme conditions and electrocatalytic activity Y. Hirai, H. Kitagawa, Nonequilibrium flow-synthesis of solid-solution alloy nanoparticles:
for methanol oxidation. Scr. Mater. 138, 22–27 (2017). From immiscible binary to high-entropy alloys. J. Phys. Chem. C 125, 458–463 (2021).
113. C. M. Rost, E. Sachet, T. Borman, A. Moballegh, E. C. Dickey, D. Hou, J. L. Jones, 139. T. Tsukamoto, T. Kambe, A. Nakao, T. Imaoka, K. Yamamoto, Atom-hybridization
S. Curtarolo, J.-P. Maria, Entropy-stabilized oxides. Nat. Commun. 6, 8485 (2015). for synthesis of polymetallic clusters. Nat. Commun. 9, 3873 (2018).
114. C. Oses, C. Toher, S. Curtarolo, High-entropy ceramics. Nat. Rev. Mater. 5, 295–309 (2020). 140. Z. Ji, T. Li, O. M. Yaghi, Sequencing of metals in multivariate metal-organic frameworks.
115. C. Deng, P. Wu, L. Zhu, J. He, D. J. Tao, L. Lu, M. He, M. Hua, H. Li, W. Zhu, High-entropy Science 369, 674–680 (2020).
oxide stabilized molybdenum oxide via high temperature for deep oxidative 141. P.-C. Chen, M. Liu, J. S. Du, B. Meckes, S. Wang, H. Lin, V. P. Dravid, C. Wolverton,
desulfurization. Appl. Mater. Today 20, 100680 (2020). C. A. Mirkin, Interface and heterostructure design in polyelemental nanoparticles. Science
116. Z. Zhang, S. Yang, X. Hu, H. Xu, H. Peng, M. Liu, B. P. Thapaliya, K. Jie, J. Zhao, J. Liu, 363, 959–964 (2019).
H. Chen, Y. Leng, X. Lu, J. Fu, P. Zhang, S. Dai, Mechanochemical nonhydrolytic sol–gel- 142. V. Fung, G. Hu, P. Ganesh, B. G. Sumpter, Machine learned features from density of states
strategy for the production of mesoporous multimetallic oxides. Chem. Mater. 31, for accurate adsorption energy prediction. Nat. Commun. 12, 88 (2021).
5529–5536 (2019). 143. V. Fung, J. Zhang, E. Juarez, B. Sumpter, Benchmarking graph neural networks for
117. H. Chen, K. Jie, C. J. Jafta, Z. Yang, S. Yao, M. Liu, Z. Zhang, J. Liu, M. Chi, J. Fu, S. Dai, materials chemistry (2021): doi:10.26434/chemrxiv.13615421.v2.
An ultrastable heterostructured oxide catalyst based on high-entropy materials: A new 144. C. A. Menning, J. G. Chen, General trend for adsorbate-induced segregation of subsurface
strategy toward catalyst stabilization via synergistic interfacial interaction. Appl. Catal. B Environ. metal atoms in bimetallic surfaces. J. Chem. Phys. 130, 174709 (2009).
276, 119155 (2020). 145. E. K. Vestergaard, R. T. Vang, J. Knudsen, T. M. Pedersen, T. An, E. Lægsgaard,
118. H. Zhu, P. Zhang, S. Dai, Recent advances of lanthanum-based perovskite oxides I. Stensgaard, B. Hammer, F. Besenbacher, Adsorbate-induced alloy phase separation:
for catalysis. ACS Catal. 5, 6370–6385 (2015). A direct view by high-pressure scanning tunneling microscopy. Phys. Rev. Lett. 95, 126101 (2005).
119. P. Edalati, Q. Wang, H. Razavi-Khosroshahi, M. Fuji, T. Ishihara, K. Edalati, Photocatalytic 146. D. Bérardan, S. Franger, A. K. Meena, N. Dragoe, Room temperature lithium superionic
hydrogen evolution on a high-entropy oxide. J. Mater. Chem. A 8, 3814–3821 (2020). conductivity in high entropy oxides. J. Mater. Chem. A 4, 9536–9541 (2016).
120. D. Wang, Z. Liu, S. Du, Y. Zhang, H. Li, Z. Xiao, W. Chen, R. Chen, Y. Wang, Y. Zou, S. Wang, 147. J. Kilner, Fast oxygen transport in acceptor doped oxides. Solid State Ionics 129, 13–23 (2000).
Low-temperature synthesis of small-sized high-entropy oxides for water oxidation. 148. F. Zhang, Y. Wu, H. Lou, Z. Zeng, V. B. Prakapenka, E. Greenberg, Y. Ren, J. Yan, J. S. Okasinski,
J. Mater. Chem. A 7, 24211–24216 (2019). X. Liu, Y. Liu, Q. Zeng, Z. Lu, Polymorphism in a high-entropy alloy. Nat. Commun. 8, 15687 (2017).
121. S. Zhai, J. Rojas, N. Ahlborg, K. Lim, M. F. Toney, H. Jin, W. C. Chueh, A. Majumdar, The use 149. C. Yang, B. H. Ko, S. Hwang, Z. Liu, Y. Yao, W. Luc, M. Cui, A. S. Malkani, T. Li, X. Wang,
of poly-cation oxides to lower the temperature of two-step thermochemical water J. Dai, B. Xu, G. Wang, D. Su, F. Jiao, L. Hu, Overcoming immiscibility toward bimetallic
splitting. Energy Environ. Sci. 11, 2172–2178 (2018). catalyst library. Sci. Adv. 6, eaaz6844 (2020).
122. H. Chen, J. Fu, P. Zhang, H. Peng, C. W. Abney, K. Jie, X. Liu, M. Chi, S. Dai, Entropy-
stabilized metal oxide solid solutions as CO oxidation catalysts with high-temperature Acknowledgments
stability. J. Mater. Chem. A 6, 11129–11133 (2018). Funding: This work was supported by the U.S. Department of Energy, Office of Science, Office
123. H. Chen, W. Lin, Z. Zhang, K. Jie, D. R. Mullins, X. Sang, S.-Z. Yang, C. J. Jafta, C. A. Bridges, of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis
X. Hu, R. R. Unocic, J. Fu, P. Zhang, S. Dai, Mechanochemical synthesis of high entropy Science Program. Author contributions: S.D. conceived the idea, and Y.S. and S.D. cowrote
oxide materials under ambient conditions: Dispersion of catalysts via entropy the paper. Competing interests: The authors declare that they have no competing interests.
maximization. ACS Mater. Lett. 1, 83–88 (2019). Data and materials availability: All data needed to evaluate the conclusions in the paper are
124. F. Okejiri, Z. Zhang, J. Liu, M. Liu, S. Yang, S. Dai, Room-temperature synthesis present in the paper and/or the materials cited herein.
of high-entropy perovskite oxide nanoparticle catalysts through ultrasonication-based
method. ChemSusChem 13, 111–115 (2020). Submitted 14 December 2020
125. T. W. Hansen, A. T. DeLaRiva, S. R. Challa, A. K. Datye, Sintering of catalytic nanoparticles: Accepted 25 March 2021
Particle migration or Ostwald ripening? Acc. Chem. Res. 46, 1720–1730 (2013). Published 12 May 2021
126. H. Chen, Y. Sun, S. Yang, H. Wang, W. Dmowski, T. Egami, S. Dai, Self-regenerative noble 10.1126/sciadv.abg1600
metal catalysts supported on high-entropy oxides. Chem. Commun. 56, 15056–15059 (2020).
127. S. Mitchell, R. Qin, N. Zheng, J. Pérez-Ramírez, Nanoscale engineering of catalytic Citation: Y. Sun, S. Dai, High-entropy materials for catalysis: A new frontier. Sci. Adv. 7, eabg1600
materials for sustainable technologies. Nat. Nanotechnol. 16, 129–139 (2021). (2021).

High-entropy materials for catalysis: A new frontier
Yifan Sun and Sheng Dai
Sci. Adv., 7 (20), eabg1600.

DOI: 10.1126/sciadv.abg1600

View the article online
https://www.science.org/doi/10.1126/sciadv.abg1600
Permissions
https://www.science.org/help/reprints-and-permissions
Use of this article is subject to the Terms of service
Science Advances (ISSN 2375-2548) is published by the American Association for the Advancement of Science. 1200 New York Avenue
NW, Washington, DC 20005. The title Science Advances is a registered trademark of AAAS.
Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim
to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

High-Entropy Materials For Catalysis

Uploaded by

Copyright:

Available Formats

High-Entropy Materials For Catalysis

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

High-Entropy Materials For Catalysis

Uploaded by

Copyright:

Available Formats

SCIENCE ADVANCES | REVIEW

MATERIALS SCIENCE Copyright © 2021

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 1 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 2 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 3 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 4 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 5 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 6 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 7 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 8 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 9 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 10 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 11 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 12 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 13 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 14 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 15 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 16 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 17 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 18 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 19 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 20 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 21 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 22 of 23

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Sun and Dai, Sci. Adv. 2021; 7 : eabg1600 12 May 2021 23 of 23

Sci. Adv., 7 (20), eabg1600.

Downloaded from https://www.science.org at University of Nottingham on June 20, 2023

Use of this article is subject to the Terms of service

You might also like