Rare Met.
(2022) 41(1):125–131
https://doi.org/10.1007/s12598-021-01760-x
ORIGINAL ARTICLE
Scalable synthesis of nanoporous high entropy alloys for
electrocatalytic oxygen evolution
Li-Hua Liu, Ning Li, Mei Han, Jing-Rui Han, Hong-Yan Liang*
Received: 27 January 2021 / Revised: 19 February 2021 / Accepted: 1 March 2021 / Published online: 12 June 2021
Ó Youke Publishing Co., Ltd. 2021
Abstract High entropy alloys (HEAs) containing five or
more equimolar components have shown promising cat-
alytic performance due to their unique chemical and
mechanical properties. However, it is still challenging to
prepare scalable and efficient nanoporous HEAs as cata-
lysts. Here, we present a facile strategy to synthesize large-
scale nanoporous HEAs particles by combing vacuum
induction melting, gas atomization, and acidic etching
procedure. The application of HEAs to energy conversion
is evaluated with electrocatalytic oxygen evolution reaction
(OER) on AlCrCuFeNi HEAs. The HEAs exhibit a low
OER overpotential of 270 mV to achieve a current density
of 10 mA
cm-2, a small Tafel slope of 77.5 mV
dec-1, and
long-term stability for over 35 h in 1 mol
L-1 KOH, which
is comparable to the state-of-the-art OER electrocatalyst
RuO2. The findings in this paper not only provide an
industrial approach to produce nanoporous HEAs powder
but also inspire the applications of HEAs as catalysts.
Keywords High entropy alloys; Gas atomization; Acidic
etching; Nanoporous AlCrFeNiCu structures; Oxygen
evolution reaction
Li-Hua Liu and Ning Li have contributed equally to this work.
Supplementary Information The online version contains
supplementary material available at https://doi.org/10.1007/s12598-
021-01760-x.
L.-H. Liu
College of Innovation & Entrepreneurship, Shanghai Jianqiao
University, Shanghai 201306, China
N. Li, M. Han, J.-R. Han, H.-Y. Liang*
School of Materials Science and Engineering, Tianjin
University, Tianjin 300350, China
e-mail: hongyan.liang@tju.edu.cn
RARE METALS
1 Introduction
Alloys containing five or more near-equimolar components
in one crystalline solid-solution phase are defined as high
entropy alloys (HEAs), which have been regarded as one of
the most popular metal materials in the last decade [1].
Owing to their multi-elemental composition, HEAs have
unique mechanical, chemical, and electromagnetic proper-
ties and show great potential for both structural and func-
tional applications [2]. The cocktail effect of HEAs arising
from tunable chemical compositions of dissimilar metal
elements provides the possibility of modulating their elec-
tronic structure, which is of great interest for optimizing their
intrinsic electrochemical catalysis activity. Moreover, the
high thermal and corrosive resistance enhances their dura-
bility in electrocatalytic environments. These advantages
made HEAs promising candidates for catalysis [3], which
have shown excellent performance in various reactions, such
as dye degradation [4], methanol oxidation [5], ammonia
decomposition [6], and water splitting [7–9].
Heterogeneous catalysts generally have a large surface-
area-to-volume ratio, which is important for exposing active
sites, enhancing mass transport and diffusion [10–14].
Porosity and nanostructure are representative features for
high surface-area-to-volume ratio morphology [15–17],
which have received widespread concern in the catalytic
area. However, traditional HEAs are made in ‘bulk’ scale
[18], and there is not enough research about translating these
bulk materials into nanoparticles (NPs) or nanoporous
structures [6, 19]. The reproducible and scalable strategies
for prepared nanoscale HEAs are highly required but still
challenging.
Top-down and bottom-up are two types of well-known
approaches for synthesizing nanoscale structures, and
several traditional methods have been taken to produce
1
126
nanosized HEAs NPs. For example, the carbothermal
shock method has been reported to fabricate multi-com-
ponent alloy NPs on a carbon support, but the synthesis
condition was quite harsh [20]. A sol–gel autocombustion
technique was developed to synthesize HEAs NPs [21].
Mechanical ball milling of single metal powders has been
used to synthesize HEAs NPs immobilized on graphene
[22, 23]. Electrosynthesis was taken to deposit HEAs NPs
with controllable components’ stoichiometry ratio [7].
Ultrashort-pulsed laser ablation was used to synthesize
colloidal HEAs NPs dispersed in a liquid solution [24].
Compared with HEAs NPs, there were fewer reports about
nanoporous HEAs’ synthesis. Generally, bottom-up tem-
plate-based synthesis and top-down dealloying methods are
two strategies for the fabrication of nanoporous structures
[25]. Dealloying Al-based alloys is an effective approach to
prepare nanoporous alloys, which have been successfully
used for traditional metallurgic synthesized HEAs catalysts
[8, 25, 26]. However, none of the above-mentioned
approaches are suitable for industrial production.
In this work, we present a facile, reproducible, and
scalable strategy to synthesize nanoporous HEAs, by
combing vacuum induction melting, gas atomization, and
acidic etching procedure. With this approach, we can
produce isolated nanoporous HEAs spheres with microm-
eter diameters in the scale of a kilogram. Their elemental
composition can be designed through precise control over
the metal stoichiometric ratio of the precursors. Our
products have clean surfaces without any ligands for sta-
bilization. The newly-developed AlCrCuFeNi HEAs with
high compressive strength and hardness were used as a
model for synthesis [27], and also for catalytic application
in electrocatalytic oxygen evolution reaction (OER)
[28, 29], which is a critical anodic reaction for several
energy conversion systems such as water splitting [30–32]
and CO2 reduction [33, 34]. The AlCrCuFeNi HEAs are
expected to show excellent OER performance because
NiFe has been widely recognized as efficient OER cata-
lysts, and Cr-doped NiFe has shown a positive effect for
OER due to introducing new active sites [35]. Moreover,
embedded Cu in NiFe can promote the formation of high-
valent Ni sites, which are active OER sites [28]. Al can be
used for dealloying to form nanoporous structures. Thus,
AlCrCuFeNi HEAs can combine both modified electronic
structures and self-constructed nanoporous structures to
boost the OER process. The effect of acidic etching was
investigated by comparing morphologies, structures, and
chemical composition to understand the evolution of the
materials. The optimized HEAs exhibit a low overpotential
of 270 mV at 10 mA
cm-2, a small Tafel slope of
77.5 mV
dec-1, and long-term stability for over 35 h in
1 mol
L-1 KOH, which is comparable to the state-of-the-
art OER electrocatalysts RuO2.
1 Rare Met. (2022) 41(1):125–131
L.-H.Liu et al.
2 Experimental
2.1 Preparation of nanoporous HEAs catalysts
The HEAs were prepared by vacuum induction melting
followed by gas atomization. The precursor alloys with a
composition of AlCrFeNiCu were mixed with a designed
stoichiometric ratio as starting material and were placed in
the crucible, which was further melted at 1750 8C using an
induction-melting furnace with a maximum output power
of 450 kW. After that, 6 MPa argon was used for gas
atomization. During this process, the high-temperature
liquid metal drops through the conduit to form droplets at
the center of the nozzle, which are ruptured by high-speed
argon and rapidly solidified into spherical particles with
micrometer size diameters. Chemical dealloying of the
HEAs spheres was carried out by soaking them in
3 mol
L-1 HNO3, and nanoporous spheres can be obtained
with varied acidic etching time. All powders were washed
with deionized water at least three times before use.
The catalyst ink was prepared by sonicating a mixture of
5 mg HEAs, 5 mg carbon black, 250 ll isopropanol,
250 ll Milli-Q ultrapure water, and 30 ll nafion solution
for at least 30 min. Then the uniform mixture was dropped
on nickel foam and dried at room temperature to form a
0.25 cm-2 effective catalytic area. The catalyst loading
was about 20 mg
cm-2.
2.2 Materials characterization
The morphologies of the prepared sample were performed on
field emission scanning electron microscopy (SEM, Hitachi
S-4800) equipped with energy-dispersive X-ray spectroscopy
(EDS) detector, and transmission electron microscopy (TEM,
JEM-2100F) also equipped with EDS detector. The phase
composition and crystal structure of the samples were exam-
ined by a powder X-ray diffractometer (XRD, Bruker D8)
using Cu Ka radiation. The surface elemental composition
and chemical states were analyzed by an X-ray photoelectron
spectrometer (XPS, Thermo ESCALAB 250XI).
2.3 Electrochemical measurements
All electrochemical tests were performed on an electro-
chemical workstation (Autolab PGSTAT302N) with a
standard three-electrode system. HEAs powder loaded on
nickel foam was used as working electrode, Ag/AgCl
electrode with saturated KCl as the filling solution, and
platinum foil was used as the reference electrode and the
counter electrode, respectively. The electrolyte was
1 mol
L-1 KOH. All applied potentials against the Ag/
AgCl reference were converted to the reversible hydrogen
electrode (RHE) through standard calibration.
Scalable synthesis of nanoporous high entropy alloys for electrocatalytic oxygen evolution
Electrochemical activation was carried out by 25 cycles
of cyclic voltammograms (CV) scans in the potential range
from 1.0 to 1.8 V (vs.RHE) at a sweep rate of 20 mV
s-1.
Linear sweep voltammetry (LSV) at a scan rate of
1 mV
s-1 was performed in the potential range from 1.0 to
1.8 V (vs. RHE) to evaluate the OER activity by collecting
the polarization curves. Tafel slopes were derived through
plotting overpotential against lgJ (where J is current den-
sity) from the linear region of the LSV polarization curves.
To correct the solution resistance, electrochemical impe-
dance spectroscopy (EIS) analysis was conducted at 0.55 V
with frequencies ranging from 0.1 Hz to 100 kHz. The
alternate current (AC) amplitude for the EIS measurement
was 5 mV. The electrochemical double-layer capacitance
(Cdl) was carried out to determine the electrochemical
active surface area (ECSA). CV scans were carried out in a
non-Faradic potential region at various scan rates ranging
from 20 to 120 mV
s-1 at a potential window of
0.92–1.02 V (vs. RHE). Cdl values were estimated by
plotting DJ = (Ja-Jc) at 0.974 V (vs. RHE) against the
scan rates. The long-term durability of the HEAs catalysts
was evaluated by a chronoamperometry experiment at an
overpotential of 290 mV.
3 Results and discussion
3.1 Morphology and physicochemical
characterization of materials
Figure 1a schematically shows the preparation process of
AlCrFeNiCu HEAs catalysts. A vacuum-induction melting
followed by a gas atomization process was applied to
synthesize scalable HEAs powders. Then, acidic etching
was used as chemical dealloying to remove the Al phase
and form a nanoporous structure. The detailed information
can be found in the experimental section. This work pro-
vides a facile strategy for synthesizing nanoporous HEAs
catalysts on a large scale, which can reach up to 200 kg in
one batch synthesis.
The morphology of HEA powders synthesized by gas
atomization was revealed by SEM, as shown in Fig. 1b.
The raw AlCrCuFeNi HEAs show a smooth spherical
outline with size distribution ranging from 4 to 6 lm. After
dealloying process, the surface was selectively etched,
resulting in uniformly distributed nanosized pores, as
shown in Fig. 1c, which can lead to a large surface area and
active site exposure during the OER process, thus facili-
tating the mass transfer. In our experiments, the etching
time was controlled to less than half an hour, thus the
dealloying process was only observed on the surface of
HEAs spheres due to its corrosive resistance, and the
porous layers were quite thin, as indicated by the following
Rare Met. (2022) 41(1):125–131
127
TEM images. Phase identification of the product was per-
formed by XRD. Figure 2a shows three diffraction peaks in
the XRD pattern, which can be ascribed to (110), (200) and
(211) planes in the bcc phase [27]. No other phases such as
the typical fcc phase were observed, confirming that our
products are single-phase solid solution, without second
phase or impurities formation during the rapid solidifica-
tion process [27]. Noted that the composition of alloy
should be well designed, and cannot be arbitrarily alloyed
in a single-phase solid solution.
The chemical compositions of HEAs before and after
etching were investigated by EDS. Before acidic etching,
all five elements distributed uniformly in AlCrCuFeNi
HEA, as shown in Fig. S1, confirming that they are mixed
well without phase separation or pure single-metal phase.
The HEAs show a near equimolar elemental ratio (Fig. S2),
which is in good agreement with the original feeding ratio.
After acidic etching, the contents of Al and Cu dramati-
cally decreased. Al was removed during the dealloying
process, and the porous structure can be obtained, as shown
in TEM images (Fig. 2b, c), which can lead to a large
surface area and active site exposure, thus facilitating the
mass transfer. TEM-EDS mapping results in Fig. 2d–i
show that all four elements, Cu, Cr, Fe and Ni distributed
homogenously, which is a typical feature of HEAs. After
dealloying, most Al elements were removed and the
residual Al shows weak signal intensity, which is consis-
tent with the low atomic percentage of Al residue in
Figs. S3, 4.
3.2 Electrocatalytic performances
The catalytic performance of HEAs powder was evaluated
by their anodic polarization curves in the OER process.
Before OER measurements, all catalysts were electro-
chemically activated by potential cycling between 1.0 and
1.8 V (vs. RHE) for 25 cycles. OER polarization curves are
shown in Fig. 3a, and the overpotentials to achieve a cur-
rent density of 10 mA
cm-2 for nickel foam, initial HEAs,
etched HEAs and commercial RuO2 were 370, 350, 270
and 260 mV, respectively. Tafel slopes calculated from
polarization curves of different samples are shown in
Fig. 3b. The initial HEAs, etched HEAs and commercial
RuO2 had a Tafel slope of 94.5, 77.5 and 72.4 mV
dec-1,
respectively. It is obvious that the OER activity of the
initial HEAs was poor, which can be greatly promoted after
acidic etching due to the formation of nanoporous struc-
ture. The effects of etching time were investigated in
Fig. S5. The results have shown that the optimized etching
time was 15 min, with an overpotential comparable to that
of commercial RuO2. When the etched time was longer
than 15 min, the electrocatalytic activity reduced. The
ECSA was investigated by electrochemical capacitance
1
128 L.-H.Liu et al.

Fig. 1 a Schematic procedure for synthesizing nanoporous AlCrFeNiCu HEAs, where inserted photo shows a batch of prepared
powder; SEM images of single-particle b before and c after acidic etching

Fig. 2 a XRD pattern of HEAs powder; b TEM image and c high-resolution TEM image of single HEA sphere; d TEM image and e–
i corresponding EDS elemental mappings for five elemental distribution

measurements in Fig. S6. LSV polarized curves normalized surface area is not the only reason for boosted OER activity
to ECSA in Fig. S6d show that the etched sample has an after acidic etching.
overpotential of 380 mV under 0.1 mA
cm-2, lower than EIS was used for exploring the surface properties,
490 mV for the initial sample, indicating that the enlarged conductivity, and electrochemical behavior of HEAs

1 Rare Met. (2022) 41(1):125–131

Scalable synthesis of nanoporous high entropy alloys for electrocatalytic oxygen evolution 129

Fig. 3 a OER polarization and b Tafel curves of prepared sample and RuO2; c EIS plots of HEAs with and without acidic etching,
where Z is impedance; d Chronoamperomery curve at overpotential of 290 mV in 1 mol
L-1 KOH

electrodes, and the Nyquist plots are shown in Fig. 3c. The
semicircles were observed in the Nyquist diagram, which
indicates the charge-transfer process at the electrode/elec-
trolyte interface. The Nyquist plot of etched HEAs shows a
smaller diameter than that of the initial one, demonstrating
the higher conductivity and beneficial OER kinetics. The
operation durability of the optimized sample was demon-
strated by OER operating at overpotential of 290 mV for
over 35 h, as shown in Fig. 3d, which is further confirmed
by the LSV curves recorded for HEAs before and after
2000 cycles in Fig.S7a and multiple current steps of
chronopotentiometry experiment in Fig.S7b.
3.3 Catalytic mechanism investigation
The nanoporous HEAs show decent catalytic performance,
and the improved intrinsic activity might be due to the
electronic effect or the synergic effect. XPS was carried out
to explore the surface composition and chemical states in
the near-surface region of nanoporous HEAs. All five metal
elements, Al, Cu, Cr, Fe and Ni are found in the survey
XPS in Fig. 4a, which is in accordance with the results of
elemental mappings. Figure 4b–f shows the fitted XPS
spectra of each element before and after OER operation.
Figure 4b shows that before OER, two peaks located at
856.1 and 973.7 eV can be assigned to Ni2? 2p3/2 and Ni2?
2p1/2, respectively. The other two peaks located at 852.6
and 869.9 eV can be assigned Ni0? 2p3/2 and Ni0? 2p1/2,
respectively. After OER, all Ni0? are oxidized, and the
Ni2? 2p peaks positively shifted by 0.1 eV, indicating the
formation of high-valent Ni sites. Figure 4c shows that
before OER process, the signals of Fe can be assigned to
Fe3?/Fe2? 2p and Fe0? 2p, respectively. After the OER
process, Fe mainly presents in the form of oxidized states,
with 0.5 eV energy shift toward the high energy direction.
A similar trend was also found in Cr, Cu and Al cases.
Both oxidized and metallic Cr, Cu and Al co-exist before
OER, and metal phases disappear completely after OER,
confirming that all metal elements are oxidized to a higher
valent state. The peak of Cr3? shows a positive energy shift
after OER process. It is interesting that the Cu2? 2p peaks
show a slightly negative energy shift after OER, which
might be caused by accepting electrons from other metals.
The Al3? 2p peaks show no significant shift after OER
process, indicating an unaffected electron structure. These
results show that after OER process, the positive shifts in
binding energy peaks of Ni2?, Fe3?/Fe2?, Cr3? happen
with the increased high-valent state, and the negative shift
of Cu2? happens, illustrating the electron transfer from
Ni2?, Fe3?, and Cr3? to Cu2? [28].

Rare Met. (2022) 41(1):125–131 1

130
Fig. 4 a Survey XPS and high-resolution XPS spectra of b Ni 2p, c Fe 2p, d Cr 2p, e Cu 2p and f Al 2p
Both Ni and Fe have been reported as active OER sites,
which can be oxidized into high-valent states during the
OER process. The doped Cr in NiFe can be oxidized into a
6? valence state as new active sites [35]. The role of Cu in
these HEAs catalysts is expected as electron acceptor due
to its high electronegativity, which has been proved in our
previous research [28]. Al shows no significant influence
on the electronic structure of other metals, it mainly favors
the formation of a nanoporous structure during the deal-
loying process. In addition, the acidic etching process can
accelerate the oxidation process, which also benefits OER
[29]. It can be concluded that the synergistic effect between
electronic structure modification and nanoporous mor-
phology formation on the HEAs surface contribute together
to the promoted OER performance.
4 Conclusion
Nanoporous AlCrCuFeNi HEAs have been synthesized
on an industrial scale by combing vacuum induction
melting, gas atomization and acidic etching procedure.
The multiple metallic products were used as OER cata-
lysts in alkaline media for an energy conversion appli-
cation. The HEAs exhibit a low OER overpotential of
270 mV to achieve a current density of 10 mA
cm-2, a
small Tafel slope of 77.5 mV
dec-1, and long-term sta-
bility for over 35 h in 1 mol
L-1 KOH, which is
1 Rare Met. (2022) 41(1):125–131
L.-H.Liu et al.
comparable to the state-of-the-art OER electrocatalyst
RuO2. The synergistic effect between electronic structure
modification and nanoporous morphology on the HEAs
surface contributes equally to the promoted OER per-
formance. This research provides direct experimental
evidence for synthesizing nanoporous HEAs powder and
exploring their application in electrochemical energy
storage and conversion.
Acknowledgments This study was financially supported by the
National Natural Science Foundation of China (No. 51771132).
References
[1] Yeh JW, Chen SK, Lin SJ, Gan JY, Chin TS, Shun TT, Tsau
CH, Chang SY. Nanostructured high-entropy alloys with mul-
tiple principal elements: novel alloy design concepts and out-
comes. Adv Eng Mater. 2004;6(5):299.
[2] Miracle DB, Senkov ON. A critical review of high entropy
alloys and related concepts. Acta Mater. 2017;122:448.
[3] Li JY, Doubek G, McMillon-Brown L, Taylor AD. Recent
advances in metallic glass nanostructures: synthesis strategies
and electrocatalytic applications. Adv Mater. 2019;31(7):
1802120.
[4] Lv ZY, Liu XJ, Jia B, Wang H, Wu Y, Lu ZP. Development of a
novel high-entropy alloy with eminent efficiency of degrading
azo dye solutions. Sci Rep. 2016;6:34213.
[5] Yusenko KV, Riva S, Carvalho PA, Yusenko MV, Arnaboldi S,
Sukhikh AS, Hanfland M, Gromilov SA. First hexagonal close
packed high-entropy alloy with outstanding stability under
Scalable synthesis of nanoporous high entropy alloys for electrocatalytic oxygen evolution
extreme conditions and electrocatalytic activity for methanol
oxidation. Scripta Mater. 2017;138:22.
[6] Xie P, Yao Y, Huang Z, Liu Z, Zhang J, Li T, Wang G,
Shahbazian-Yassar R, Hu L, Wang C. Highly efficient decom-
position of ammonia using high-entropy alloy catalysts. Nat
Commun. 2019;10(1):4011.
[7] Glasscott MW, Pendergast AD, Goines S, Bishop AR, Hoang
AT, Renault C, Dick JE. Electrosynthesis of high-entropy
metallic glass nanoparticles for designer, multi-functional elec-
trocatalysis. Nat Commun. 2019;10:2650.
[8] Jin Z, Lv J, Jia H, Liu W, Li H, Chen Z, Lin X, Xie G, Liu X,
Sun S, Qiu HJ. Nanoporous Al–Ni–Co–Ir–Mo high-entropy
alloy for record-high water splitting activity in acidic environ-
ments. Small. 2019;15(47):e1904180.
[9] Zhang G, Ming K, Kang J, Huang Q, Zhang Z, Zheng X, Bi X.
High entropy alloy as a highly active and stable electrocatalyst
for hydrogen evolution reaction. Electrochim Acta. 2018;279:
19.
[10] Huang AQ, He YZ, Zhou YZ, Zhou YY, Yang Y, Zhang JC,
Luo L, Mao QM, Hou DM, Yang J. A review of recent appli-
cations of porous metals and metal oxide in energy storage,
sensing and catalysis. J Mater Sci. 2019;54(2):949.
[11] Sudarsanam P, Peeters E, Makshina EV, Parvulescu VI, Sels BF.
Advances in porous and nanoscale catalysts for viable biomass
conversion. Chem Soc Rev. 2019;48(8):2366.
[12] Liang HY, Wei H, Pan D, Xu H. Chemically synthesized noble
metal nanostructures for plasmonics. Nanotechnol REV. 2015;
4(3):289.
[13] Liang HY, Yuan F, Johnston A, Gao C, Choubisa H, Gao Y,
Wang YK, Sagar LK, Sun B, Li P, Bappi G, Chen B, Li J, Wang
Y, Dong Y, Ma D, Gao Y, Liu Y, Yuan M, Saidaminov MI,
Hoogland S, Lu ZH, Sargent EH. High color purity lead-free
perovskite light-emitting diodes via Sn stabilization. Adv Sci.
2020;7(8):1903213.
[14] Tong X, Liang HY, Liu Y, Tan L, Ma D, Zhao Y. Anisotropic
optical properties of oriented silver nanorice and nanocarrots in
stretched polymer films. Nanoscale. 2015;7(19):8858.
[15] Liang HY, Zhao HG, Li ZP, Harnagea C, Ma DL. Silver
nanoparticle film induced photoluminescence enhancement of
near-infrared emitting PbS and PbS/CdS core/shell quantum
dots: observation of different enhancement mechanisms.
Nanoscale. 2016;8(9):4882.
[16] Wang N, Miao RK, Lee G, Vomiero A, Sinton D, Ip AH, Liang
HY, Sargent EH. Suppressing the liquid product crossover in
electrochemical CO2 reduction. SmartMat. 2021. https://doi.org/
10.1002/smm2.1018.
[17] Liang HY, Wei H, Xu HX. Deviating from the nanorod shape:
Shape-dependent plasmonic properties of silver nanorice and
nanocarrot structures. Front Phys. 2016;11(2):117301.
[18] Torralba JM, Alvaredo P, Garcia-Junceda A. High-entropy
alloys fabricated via powder metallurgy. A critical review.
Powder Metall. 2019;62(2):84.
[19] Wu QF, Wang ZJ, He F, Wang LL, Luo J, Li JJ, Wang JC. High
entropy alloys: from bulk metallic materials to nanoparticles.
Metall Mater Trans A. 2018;49A(10):4986.
[20] Yao YG, Huang ZN, Xie PF, Lacey SD, Jacob RJ, Xie H, Chen
FJ, Nie AM, Pu TC, Rehwoldt M, Yu DW, Zachariah MR,
Wang C, Shahbazian-Yassar R, Li J, Hu LB. Carbothermal
Rare Met. (2022) 41(1):125–131
131
shock synthesis of high-entropy-alloy nanoparticles. Science.
2018;359(6383):1489.
[21] Niu B, Zhang F, Ping H, Li N, Zhou JY, Lei LW, Xie JJ, Zhang
JY, Wang WM, Fu ZY. Sol-gel autocombustion synthesis of
nanocrystalline high-entropy alloys. Sci Rep. 2017;7(1):3421.
[22] Dai WJ, Lu T, Pan Y. Novel and promising electrocatalyst for
oxygen evolution reaction based on MnFeCoNi high entropy
alloy. J Power Sources. 2019;430:104.
[23] Cui XD, Zhang BL, Zeng CY, Guo SM. Electrocatalytic activity
of high-entropy alloys toward oxygen evolution reaction. MRS
Commun. 2018;8(3):1230.
[24] Waag F, Li Y, Ziefuss AR, Bertin E, Kamp M, Duppel V,
Marzun G, Kienle L, Barcikowski S, Gokce B. Kineti-
cally-controlled laser-synthesis of colloidal high-entropy alloy
nanoparticles. RSC Adv. 2019;9(32):18547.
[25] Qiu HJ, Fang G, Wen YR, Liu P, Xie GQ, Liu XJ, Sun SH.
Nanoporous high-entropy alloys for highly stable and efficient
catalysts. J Mater Chem A. 2019;7(11):6499.
[26] Qiu HJ, Fang G, Gao JJ, Wen YR, Lv J, Li HL, Xie GQ, Liu XJ,
Sun SH. Noble metal-free nanoporous high-entropy alloys as
highly efficient electrocatalysts for oxygen evolution reaction.
ACS Mater Lett. 2019;1(5):526.
[27] Luo SC, Gao P, Yu HC, Yang JJ, Wang ZM, Zeng XY.
Selective laser melting of an equiatomic AlCrCuFeNi high-en-
tropy alloy: processability, non-equilibrium microstructure and
mechanical behavior. J Alloys Compd. 2019;771:387.
[28] Han M, Wang N, Zhang B, Xia YJ, Li J, Han JR, Yao KL, Gao
CC, He CN, Liu YC, Wang ZM, Seifitokaldani A, Sun XH,
Liang HY. High-valent nickel promoted by atomically embed-
ded copper for efficient water oxidation. ACS Catal. 2020;
10(17):9725.
[29] Han M, Li SC, Li C, Wu J, Han JR, Wang N, Liu YC, Liang HY.
Strain-modulated Ni3Al alloy promotes oxygen evolution reac-
tion. J Alloys Compd. 2020;844:156094.
[30] Chen YZ, Jiang DJ, Gong ZQ, Li JY, Wang LN. Anodized metal
oxide nanostructures for photoelectrochemical water splitting.
Int J Min Met Mater. 2020;27(5):584.
[31] Ding WL, Cao YH, Liu H, Wang AX, Zhang CJ, Zheng XR.
In situ growth of NiSe@Co0.85Se heterointerface structure with
electronic modulation on nickel foam for overall water splitting.
Rare Met. 2020;39(1):1.
[32] Wang ZY, Jiang SD, Duan CQ, Wang D, Luo SH, Liu YG.
In situ synthesis of Co3O4 nanoparticles confined in 3D nitro-
gen-doped porous carbon as an efficient bifunctional oxygen
electrocatalyst. Rare Met. 2020;39(12):1383.
[33] Zhu M, Ge QF, Zhu XL. Catalytic reduction of CO2 to CO via
reverse water gas shift reaction: recent advances in the design of
active and selective supported metal catalysts. Trans Tianjin
Univ. 2009;26(3):172.
[34] Yao KL, Xia YJ, Li J, Wang N, Han JR, Gao CC, Han M, Shen
GQ, Liu YC, Seifitokaldani A, Sun XH, Liang HY. Metal-or-
ganic framework derived copper catalysts for CO2 to ethylene
conversion. J Mater Chem A. 2020;8(22):11117.
[35] Bo X, Hocking RK, Zhou S, Li YB, Chen XJ, Zhuang JC, Du Y,
Zhao C. Capturing the active sites of multimetallic (oxy)hy-
droxides for the oxygen evolution reaction. Energ Environ Sci.
2020;13(11):4225.
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