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Two-Dimensional High-Entropy Metal

Phosphorus Trichalcogenides for Enhanced
Hydrogen Evolution Reaction
Ran Wang, Jinzhen Huang, Xinghong Zhang, Jiecai Han, Zhihua Zhang, Tangling Gao, Lingling Xu,
Shengwei Liu, Ping Xu, and Bo Song*
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ABSTRACT: Developing earth-abundant and highly effective electrocatalysts for

hydrogen evolution reaction (HER) is a prerequisite for the upcoming hydrogen
energy society. Two-dimensional (2D) high-entropy metal phosphorus trichalcoge-
nides (MPCh3) have the advantages of both near-continuous adsorption energies of
high-entropy alloys (HEAs) and large specific surface area of 2D materials, which are
excellent catalytic platforms. As a typical 2D high-entropy catalyst,
Co0.6(VMnNiZn)0.4PS3 nanosheets with high-concentration active sites are success-
fully demonstrated to show enhanced HER performance: an overpotential of 65.9
mV at a current density of 10 mA cm−2 and a Tafel slope of 65.5 mV dec−1. Decent
spectroscopy characterizations are combined with density function theory analyses to
show the scenario for the enhancement mechanism by a high-entropy strategy. The optimized S sites on the edge and P sites
on the basal plane provide more active sites for hydrogen adsorption, and the introduced Mn sites boost water dissociation
during the Volmer step. Two-dimensional high-entropy MPCh3 provides an avenue for the combination of HEAs and 2D
materials to enhance the HER performance, which also provides an alternative materials platform to explore and design
superior catalysts for various electrochemical systems.
KEYWORDS: 2D materials, high-entropy, hydrogen evolution reaction, metal phosphorus trichalcogenides, electrocatalysis

INTRODUCTION
Hydrogen is a carbon-neutral fuel that promises to replace
traditional fossil fuels to cope with the increasing greenhouse
effect.1 Hydrogen evolution reaction (HER) in the cathode
plays a key role in electrocatalysis water splitting, which can
effectively convert green electricity into renewable hydrogen
energy. Although noble metals (Pt,2,3 Ru,4 Rh,5etc.) have
impressive HER activities, their large-scale application is limited
by high cost and low elemental abundance. Developing high-
performance while cost-effective HER catalysts based on non-
noble elements is still highly desirable.6 Recently, various earth-
abundant transition metal compounds have been identified as
promising HER catalysts, including metal nitride,7,8 metal
sulfide,9,10 metal phosphide,11 and metal phosphosulfide.12
Among them, the two-dimensional (2D) metal phosphorus
trichalcogenides (MPCh3) are widely investigated as a
promising catalytic platform with high specific surface area,
good physicochemical characteristics, tunable charge states, and
appropriate band structures.13,14 Although they have similar
functional groups of [PxSy]4−,15,16 the intrinsic activity of
MPCh3 is still limited by the improper electron distribution.
Theoretical calculations reveal that only the edge sites in MPCh3
are active,17 while the sites at the basal plane remain less active
toward HER.18 To regulate the activity of adsorption sites on the
basal plane, unary or binary doping with only a few elements
could be an alternative method, but the lack of broad
composition is adverse for further improvements in perform-
ance.19,20 Thus, introducing multiple metal elements to achieve
continuous tunability for optimal adsorption of reaction
intermediates is intuitively a better strategy but remains
unexplored.
As a class of materials system, high-entropy alloys (HEAs)
have attracted wide interest in the past few years due to their
mechanical properties and potential applications.21−25 In
contrast to the traditional multicomponent alloys with one or
two principal elements, HEAs are a kind of alloying strategy that
involves the combination of five or more elements in a relatively
Received: January 30, 2022
Accepted: February 23, 2022
Published: February 25, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acsnano.2c01064

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high concentration (5−35 at. %).26,27 Because of the abundant
elemental composition, HEAs can provide an extensive
combinatorial space for designing high-performance cata-
lysts.28−30 Moreover, the continuously tunable adsorption
energies of HEAs also optimize the kinetic barrier for the
adsorption/desorption of reaction intermediates and thus
increase the catalytic performance.31,32 However, the HEAs
prepared by traditional methods are bulk materials rather than
nanostructures.33,34 The limited exposure of active sites makes it
difficult to further improve the catalytic performance.35
Although the preparation of uniform nanostructured HEAs
with specific equipment and high temperature with fast heating/
cooling rate has been proposed,36−40 achieving a large
electrochemical active area and full utilization of active sites in
HEAs is still challenging.41,42
Considering both the advantage (layered morphology) and
disadvantage (less active basal plane) of MPCh3, we apply the
high-entropy strategy to the 2D MPCh3 system and demonstrate
the successful synthesis of Co0.6(VMnNiZn)0.4PS3 nanosheets
(NSs) with monoclinic structure and high surface area (Figure
1a and b). The Co0.6(VMnNiZn)0.4PS3 NSs achieve a low
overpotential (η) of 65.9 mV at the current density of 10 mA
cm−2 and a Tafel slope of 65.5 mV dec−1. To our knowledge, it is
promising that a high-entropy strategy is applied to 2D materials
for the HER process, and the HER performance of
Co0.6(VMnNiZn)0.4PS3 NSs is one of the best among the
Figure 1. DFT calculation on the edge mode. (a) Crystal structure of
CoVMnNiZnPS3 with monoclinic structure (C2/m), and (b) the
structural polymorphs of CoPS3 and CoVMnNiZnPS3 along the top
views, respectively. (c) Selection strategy of the element in MPCh3.
(d) Edge models of Co, P, and S sites for CoVMnNiZnPS3 and
CoPS3, respectively. (e) HER free-energy diagram of corresponding
edge sites in (d).
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reported MPCh3 catalysts. The key merits of
Co0.6(VMnNiZn)0.4PS3 NSs are the optimized S sites on the
edge, P sites on the basal plane, and also the introduced Mn sites
on the edge for efficient water dissociation. These findings
provide an avenue for designing HER electrocatalysts with high
performance based on high-entropy 2D materials.
RESULTS AND DISCUSSION
The free energy for hydrogen chemisorption (ΔGH*) is an
effective descriptor to correlate the theoretical predictions with
experimental catalytic activities of the hydrogen evolution
systems.1 To evaluate the potential of the high-entropy strategy
for improving the HER electrocatalytic activity of MPCh3,
density function theory (DFT) calculations were performed to
investigate the difference of ΔGH* in normal and high-entropy
MPCh3.43 Given the structural stabilization and compositional
simplification, the approximately equimolar alloys of Co, V, Mn,
Ni, and Zn phosphorus trichalcogenides (CoVMnNiZnPS3)
were chosen as the representative model of high-entropy
MPCh3 (Figure 1c), and CoPS3 was considered as a control
model. The edge is regarded as a candidate for an electrocatalytic
active site in MPCh3, as shown in Figure 1d. The ΔGH* values of
0.79, 0.30, and −0.31 eV are obtained for Co, P, and S sites of
CoPS3 (Figure 1e), respectively, which suggest that the anion
sites (P and S) have better adsorption properties than the cation
sites (Co). Interestingly, when single metal Co sites are replaced
by multiple metal atoms to form CoVMnNiZnPS3, positive
shifts of ΔGH* values are observed in P (from 0.30 to 0.35 eV)
and S (from −0.31 to −0.17 eV) sites (Figure 1e), respectively,
suggesting that the S sites at the edge in CoVMnNiZnPS3 are
more favorable for the HER process.
To verify the aforementioned prediction, high-entropy and
single-cation MPCh3 NSs were prepared through a conventional
solid-state reaction (see Experimental Section) followed by
ultrasonication-assisted exfoliation (Figure S1, Supporting
Information). Because of the much lower formation enthalpy
than the configurational entropy in high-entropy MPCh3,44,45
the single-phase monoclinic structure (C2/m) with high
crystallinity inherited from the component is expected, which
is proved by the powder X-ray diffraction (PXRD) pattern
(Figures S2 and S3, Supporting Information).46 A more flexible
composition was present in Cox(VMnNiZn)1−xPS3, allowing the
ratio of Co (x) to be adjusted from 0.2 to 1.0 (Figure S4,
Supporting Information). Taking Co0.6(VMnNiZn)0.4PS3 and
CoPS3 as representative examples, scanning electron micros-
copy (SEM) images displayed the typical layered morphology of
bulk samples with a size of ∼5 μm (Figure S5a and b, Supporting
Information), and the resultant NSs after exfoliating for 3 h also
preserved the lamellar morphology (Figure S5c and d,
Supporting Information). Transmission electron microscopy
(TEM) images further revealed the similar layered morphology
in both Co0.6(VMnNiZn)0.4PS3 (Figure 2a) and CoPS3 NSs
(Figure S6, Supporting Information) with a lateral dimension of
∼400−500 nm. Selected area electron diffraction (SAED)
patterns demonstrated their good crystallinity (inset of Figures
2a and S6, Supporting Information), well consistent with the
corresponding PXRD patterns (Figure S4, Supporting Informa-
tion). The as-prepared NSs are about three to four atomic layers,
as the average thickness of Co0.6(VMnNiZn)0.4PS3 NSs is ∼2.8
± 0.7 nm, determined from the atomic force microscopy (AFM)
measurement with the Gauss function fitting (Figure 2b and c).
As shown in the high-resolution TEM (HRTEM) image (Figure
2d), the lattice spacings of 0.167 and 0.173 nm were ascribed to
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Figure 2. Structural characterizations of Co0.6(VMnNiZn)0.4PS3 and CoPS3 NSs. (a) TEM image, SAED pattern (inset of (a)), (b) AFM image,
and (c) statistical analysis from the AFM image of as-synthesized Co0.6(VMnNiZn)0.4PS3 NSs. HRTEM images of (d) Co0.6(VMnNiZn)0.4PS3
and (e) CoPS3 NSs. (f) EDS mapping images of Co0.6(VMnNiZn)0.4PS3 NSs.

Figure 3. Crystal structure analyses on Cox(VMnNiZn)1−xPS3 bulk samples. (a) Plots of the lattice constant a as a function of the ratio of Co (x).
(b) Plots of the fwhm for the (001) diffraction peak as a function of the ratio of Co (x); the inset is the enlarged (001) peak of CoVMnNiZnPS3
and CoPS3. (c) Lattice strains (ε) obtained by W−H analysis that were extracted from the plots of β cos θ as a function of 4 sin θ. (d) Plots of the
P−P bond length as a function of the Co (x).

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Figure 4. Electrochemical characterizations of Cox(VMnNiZn)1−xPS3 NSs. (a) LSV curves, (b) corresponding Tafel plots, (c) Cdl extracted from
the CV plots, and (d) overpotentials at the current density of 10 mA cm−2 (left) and the exchange current densities (right). (e) LSV curves
recorded at 25−65 °C and (f) corresponding Aapp data point and error bar of both Co0.6(VMnNiZn)0.4PS3 and CoPS3 NSs.

(330) and (060) planes of Co0.6(VMnNiZn)0.4PS3 NSs,
respectively, which were slightly larger than that of CoPS3 NSs
(d330 = 0.161 and d060 = 0.170 nm), suggesting lattice expansion
in high-entropy NSs.17 Moreover, compared with CoPS3 NSs
(inset of Figure 2e), the atomic-scale disorder from multiple
transition metals was clearly observed in Co0.6(VMnNiZn)0.4PS3
NSs (inset of Figure 2d), as revealed by the random distribution
in the intensity of atomic columns that is approximately
proportional to the squared atomic number (∼Z2).47,48 Energy-
dispersive X-ray spectroscopy (EDS) mapping showed a
homogeneous spatial distribution of Co, V, Mn, Ni, Zn, P, and
S elements throughout Co0.6(VMnNiZn)0.4PS3 NSs (Figure 2f),
further confirming no phase segregation.
To shed light on the impacts of the high-entropy strategy on
the crystal structures, we used the PXRD data of bulk MPCh3 to
evaluate the structural features and strain distribution in the
corresponding NSs. Decreasing the Co content from 0.8 to 0.2
in Cox(VMnNiZn)1−xPS3, a closer view at the (001) peak at the
2θ range of 13.25−14.25° reveals a continuous shift to lower
angle relative to that of CoPS3 (Figure S4, Supporting
Information).49 The lattice constant a also exhibits a tendency
to increase from 5.901 Å to 5.937 Å (Figure 3a), indicating a
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lattice expansion, which is well consistent with HRTEM results.
Moreover, the strains in pristine CoPS3 and high-entropy
Cox(VMnNiZn)1−xPS3 (x = 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, and 0.8)
bulk samples were further investigated by the full width at half-
maximum (fwhm) and Williamson−Hall (W−H) analysis. The
fwhm of the (001) diffraction peak in CoPS3 (0.083°) and
CoVMnNiZnPS3 (0.132°) convincingly demonstrated that the
high-entropy strategy distorted the lattices in MPCh3 (Figures
3b and S7, Supporting Information).50 The lattice strains (ε)
were calculated based on W−H analysis by using the fwhm of
the representative peaks (Figure 3c). A positive slope was
observed for all samples, as calculated from β cos θ and 4 sin θ,
revealing the presence of tensile strain in all the high-entropy
samples.51 The ε values indicate that high entropy quintuples
the lattice strains from 0.068% to 0.337%. Clearly, the mismatch
of atomic size with random distribution in high-entropy
Cox(VMnNiZn)1−xPS3 distorts the lattice. To deepen the
understanding of the crystal features of high-entropy samples,
the Rietveld refinement of PXRD data for bulk
Cox(VMnNiZn)1−xPS3 samples was performed by using the
FullProf software package (Figure S8 and Table S1, Supporting
Information).52 It was found that the P−P bond length and the
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Figure 5. Surface-chemical state characterizations on Co0.6(VMnNiZn)0.4PS3, CoPS3, VPS3, MnPS3, NiPS3, and ZnPS3 NSs. XPS spectra for (a)
Co, (b) V, (c) Mn, (d) Ni, and (e) Zn. (f) Binding energy of P and S 2p3/2 orbitals, respectively.
content of Co (x) in Cox(VMnNiZn)1−xPS3 displayed a
“volcano” relationship (Figure 3d). Obviously, a longer P−P
bond distance was observed in high-entropy
Cox(VMnNiZn)1−xPS3 compared with CoPS3, increasing from
1.851 Å to 2.120 Å. The tunable P−P bond length suggests that
the local electronic structure of P sites in MPCh3 could be
regulated via the high-entropy strategy, which may lead to a
redistribution of the electron density at each P center and make
them the promising electrocatalytic active sites toward HER.
To verify the advantages of the high-entropy strategy in
MPCh3 NSs, the HER performance was measured using a
typical three-electrode configuration in a 1 M KOH aqueous
solution with iR correction (Table S2, Supporting Information).
As expected, Co0.6(VMnNiZn)0.4PS3 NSs exhibited enhanced
HER performances with an optimum η of 65.9 mV at the current
density of 10 mA cm−2 and a Tafel slope of 65.5 mV dec−1
(Figure 4a and b) among a series of MPCh3 NSs (Figure S9,
Supporting Information), which made it one of the best catalysts
among the reported MPCh3 (Table S3, Supporting Informa-
tion). Furthermore, the electrochemical impedance spectrosco-
py (EIS) data were fitted with a Randles circuit (inset in Figures
S9 and S10, Supporting Information) to extract the resistance
(F i gu r e s S 9 an d S 1 0, S upporting I nformation).
Co0.6(VMnNiZn)0.4PS3 NSs showed lower charge transfer
resistance (Rct) (4.8 Ω), confirming its fast electron transfer
characteristic between electrolyte and catalyst.53 To extract the
electrochemical active surface area (ECSA) for the HER
process, the double-layer capacitance (Cdl) was calculated via
an analysis of cyclic voltammetry (CV) data (Figure S11,
Supporting Information). The Cdl of Co0.6(VMnNiZn)0.4PS3
(16.5 mF cm−2) NSs is larger than those of CoVMnNiZnPS3
(10.6 mF cm−2), Co0.4(VMnNiZn)0.6PS3 (13.0 mF cm−2),
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Co0.8(VMnNiZn)0.2PS3 (9.7 mF cm−2), and CoPS3 (7.9 mF
cm−2) NSs (Figure 4c), demonstrating more catalytic active sites
exposed in Co0.6(VMnNiZn)0.4PS3 NSs.54 As an inherent
parameter of HER activity, the exchange current density (j0)
was determined from the intercept of log jvs potential.50 The j0
values of 0.33, 0.82, 0.94, 0.20, and 0.06 mA cm−2 could be
obtained for CoVMnNiZnPS 3 , Co 0.4 (VMnNiZn) 0.6 PS 3 ,
Co0.6(VMnNiZn)0.4PS3, Co0.8(VMnNiZn)0.2PS3, and CoPS3
NSs, respectively (Figure 4d). The j0 for Co0.6(VMnNiZn)0.4PS3
NSs (0.94 mA cm−2) is at least ∼15 times higher than that of
CoPS 3 NSs (0.06 mA cm −2 ), suggesting a significant
contribution of high entropy to enhance the intrinsic catalytic
activity. The Co0.6(VMnNiZn)0.4PS3 NSs also showed a high
stability over 3000 CV cycles and a 12 h test at 25 and 65 °C
(Figure S12, Supporting Information), only with a small loss of
electrocatalytic activity that may be caused by a slight
mechanical drop of the catalyst during HER.
To better understand the origin of the enhanced catalytic
activity, the temperature-dependent kinetic analysis was
conducted by linear sweep voltammetry (LSV) in 1 M KOH
aqueous solution in the temperature range of 25−65 °C (Figure
S13, Supporting Information).55 It was found that with an
increase in temperature the catalytic performance gradually
enhanced (Figure 4e). The pre-exponential factor (Aapp) and
activation energy (Eapp) were calculated by the Arrhenius
equation around the onset potential of the respective samples
(Figure S14, Supporting Information). Compared with CoPS3
NSs, the maxima of both Aapp and Eapp were observed around a
lower η in Co0.6(VMnNiZn)0.4PS3 NSs (Figures 4f and S15,
Supporting Information).56 The higher Aapp suggests that the
catalytic active sites in Co0.6(VMnNiZn)0.4PS3 NSs are
enhanced by modifying the entropy of activation, which allows
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Figure 6. (a) Basal-plane models of P sites (P1−P3) and S sites (S1−S9) in Co0.6(VMnNiZn)0.4PS3. (b) HER free-energy diagram of
corresponding sites in (a). (c) Calculated charge-density difference of the P1 site for Co0.6(VMnNiZn)0.4PS3. The red and blue regions refer to
electron accumulation and depletion, respectively. (d) Calculated reaction energy of water dissociation for Co0.6(VMnNiZn)0.4PS3 and CoPS3,
including Co, V, Mn, Ni, and Zn sites.
more active sites to participate in the HER process, as the
predominance on the HER kinetics significantly influences the
reaction rate. Meanwhile, the increased reaction entropy needs a
higher Eapp as reaction enthalpy to compensate for the change in
binding energy, due to the stable enthalpy−entropy compensa-
tion effect in alkaline pH condition at both normal and high
temperatures (Figure S12, Supporting Information).55 Com-
prehensively considering the above electrochemical character-
izations, it can be concluded that the high-entropy strategy
enhanced the HER performance by modifying the reaction
entropy and increasing the abundance of active sites during HER
in Co0.6(VMnNiZn)0.4PS3 NSs.
To probe the surface chemical status, high-resolution X-ray
photoelectron spectroscopy (XPS) measurements were per-
formed on Co0.6(VMnNiZn)0.4PS3 NSs and the corresponding
single-metal MPCh3 (CoPS3, VPS3, MnPS3, NiPS3, and ZnPS3)
NSs as displayed in Figures 5 and S16. The valence-state
proportions of each metal are summarized in Table S4. The
spin−orbit 2p3/2 and 2p1/2 orbitals of Co modes are observed at
binding energies of 779.76 and 795.06 eV (Figure 5a).57−59 In
both CoPS3 and Co0.6(VMnNiZn)0.4PS3 NSs, the existence of a
doublet splitting of the Co 2p peaks is attributed to the oxidation
state of Co3+ (779.66/794.76 eV) and Co2+ (781.16/796.36
eV), respectively.60−62 In the V 2p spectrum, the mode at 514.18
eV belongs to V 2p3/2 (V3+) and the mode at 521.98 eV
corresponds to V 2p1/2 (V3+) (Figure 5b). The adjacent modes
at 516.78 eV (V 2p3/2) and 524.68 eV (V 2p1/2) are attributed to
the presence of V4+.63 The Mn 2p3/2 and Mn 2p1/2 orbital modes
are located at 640.95 and 652.86 eV, respectively, which can be
divided into Mn2+ (640.66/652.16 eV) and Mn3+ (641.96/
653.46 eV) (Figure 5c), respectively.64,65 The Ni XPS spectrum
of Co0.6(VMnNiZn)0.4PS3 NSs displays two spin−orbit doublets
and two shakeup satellites,66,67 including a Ni2+ doublet at
854.36 (Ni 2p3/2) and 871.86 (Ni 2p1/2) eV68 and a Ni3+ doublet
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at 855.76 (Ni 2p3/2) and 873.86 (Ni 2p1/2) eV (Figure 5c).69 In
contrast, the Zn XPS spectrum in ZnPS3 presents only one pair
of spin−orbit doublets at 1022.06 (2p3/2) and 1045.06 (2p1/2)
eV without a shakeup satellite (Figure 5e), which is attributed to
Zn 2 + . 7 0 Howe ve r, th e b indin g e ner gy of Zn in
Co0.6(VMnNiZn)0.4PS3 NSs is higher than that in ZnPS3 NSs.
Considering the valence-state ratio and binding-energy shift in
Co0.6(VMnNiZn)0.4PS3 NSs compared with the single-metal
MPCh3, a trend of electron deficiency states in Co and V
indicates the electron density redistribution in high-entropy
NSs.71−73 For the nonmetal element, both P and S exhibit the
lowest binding energy in Co0.6(VMnNiZn)0.4PS3 NSs compared
with those in single-metal MPCh3 NSs (Figure 5f), confirming a
higher electron-donating character of [P2S6]4− anions, which
should act as the catalytic active sites and show better hydrogen
adsorption during HER.
To verify the stability of the high-entropy structure in MPCh3
during HER, a series of postreaction characterizations were
performed on Co0.6(VMnNiZn)0.4PS3 NSs after a long-term
chronopotentiometry test at 10 mA cm−2 in 1 M KOH aqueous
solution. The TEM image (Figure S17a, Supporting Informa-
tion), SAED patterns (inset of Figure S17a, Supporting
Information), HRTEM image (Figure S17b, Supporting
Information), and EDS mapping (Figure S17c, Supporting
Information) showed that the lamellar morphology of
Co0.6(VMnNiZn)0.4PS3 NSs was preserved, which demonstra-
ted effective exposure of active sites on the catalyst surface
during the HER process. Moreover, the stability of the crystal
structure and surface chemical status of Co0.6(VMnNiZn)0.4PS3
NSs was also verified according to PXRD (Figure S18a,
Supporting Information) and XPS characterizations (Figure
S18b−h, Supporting Information). Since it is known that the
surface of some metal chalcogenides partially dissolves under
alkaline HER conditions,74 we used inductively coupled plasma
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mass spectrometry (ICP-MS) to monitor the catalyst dis-
solution rate of the high-performance Co0.6(VMnNiZn)0.4PS3
NSs during a 12 h chronopotentiometry test at 25 and 65 °C,
respectively (Table S5, Supporting Information). 7 5
Co0.6(VMnNiZn)0.4PS3 NSs displayed low dissolution ratios at
both normal and high temperatures. Comprehensively consid-
ering these postreaction characterizations, it can be concluded
that Co0.6(VMnNiZn)0.4PS3 NSs have good stability during
alkaline HER.
To build a better understanding of the fundamental
mechanism for enhanced HER catalytic activity, we further
focus on the DFT simulations to study the basal plane of the
catalyst, with the geometry mode optimized by the refinement
PXRD data. The detailed local structures on possible proton
acceptors and corresponding calculated ΔGH* are exhibited in
Figure 6a and b, respectively. As a reference, both P (1.24 eV)
and S (0.63 eV) sites on the basal plane of CoPS3 were calculated
(Figure S19, Supporting Information), while the more positive
ΔGH* values imply a weak hydrogen adsorption strength,
suggesting its surface is less active toward the HER process.
Interestingly, in the case of high-entropy, hydrogen adsorptions
on P sites (P1−P3) are generally better than those of S sites
(S1−S9), and even the P1 site is found to have a near-
thermoneutral ΔGH* value of 0.09 eV, suggesting that
introducing high entropy could effectively activate the basal
plane of Co0.6(VMnNiZn)0.4PS3. To further explain the impact
of charge redistribution on hydrogen adsorption, the charge-
density differences of Co0.6(VMnNiZn)0.4PS3 and CoPS3
models near active P1 sites were also calculated, as illustrated
in Figures 6c and S20, respectively. The electron accumulation
on P sites and the electron depletion on S sites indicate that the
electrons transfer from S to P atoms, which is beneficial to
optimize the P−H, thereby lowing ΔGH*. Moreover, the
number of transferred electrons was calculated by the Mulliken
charge analysis method. Compared with CoPS 3 ,
Co0.6(VMnNiZn)0.4PS3 showed more transferred electrons
(0.51 e−) among the P1 sites (Table S6, Supporting
Information), which agrees well with free energy evolution
results.76 Due to the catalyst working in an alkaline solution, the
water dissociation barriers of various metal sites on the edge
were also performed by DFT calculation (Figure 6d). It is shown
that the energy barrier of 0.69 eV (Mn sites, inset of Figure 6d)
for Co0.6(VMnNiZn)0.4PS3 to dissociate a water molecule is
lower than that of Co sites in CoPS3 (1.21 eV), suggesting that
metal site diversification promotes the water dissociation
kinetics during the Volmer step.77 Thus, the calculation results
prove that the enhanced HER activity in high-entropy MPCh3
originates from the synergistic effects of abundant active sites
endowed from the high-entropy strategy, with optimized S sites
on the edge and P sites on the basal plane providing more active
sites for hydrogen adsorption, as well as the introduced Mn sites
on the edge as an efficient water dissociation center.
CONCLUSIONS
In conclusion, combining high-entropy and 2D material
concepts, we have systematically investigated the HER proper-
ties of a series 2D high-entropy MPCh 3 and proved
Co0.6(VMnNiZn)0.4PS3 NSs to be one of the best catalysts
among reported MPCh3, with a low η of 65.9 mV at a current
density of 10 mA cm−2 and a Tafel slope of 65.5 mV dec−1.
Decent spectroscopy characterizations combined with DFT
calculation results suggest a redistribution of electron density
among the [P2S6]4− anions in the high-entropy samples, which
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optimize the hydrogen adsorption energy of S sites on the edge
and P sites on the basal plane. Furthermore, diversified metal
sites (especially Mn sites) on the edge boost water dissociation
in Co0.6(VMnNiZn)0.4PS3 NSs during the HER process. In all,
the high-entropy strategy increases the abundance of active sites
with continuous tenability and optimal adsorption for reaction
intermediates and thus enhances the alkaline HER performance.
This work not only demonstrates the successful application of
the HEA concept in phosphosulfide material systems but also
provides a strategy to enhance the electrocatalytic activity for 2D
catalysts.
EXPERIMENTAL SECTION
Materials. The phosphorus powder (99.99%), sulfur powder
(99.99%), cobalt powder (99.999%), vanadium powder (99.999%),
manganese (99.999%), iron (99.999%), nickel (99.999%), and zinc
powder (99.999%) were purchased from Alfa Aesar. Benchmark 20 wt
% Pt/C catalysts were purchased from Aladdin. All chemicals were of
analytical grade and were used as received without purification, unless
otherwise specified.
Synthesis of High-Entropy MPCh3 NSs. Bulk high-entropy
MPCh3 samples were prepared by traditional solid-state reaction with
their nominal composition powders (total mass of 1 g). Before the
solid-state reaction, the elemental powder was ground uniformly to
ensure the reaction happens sufficiently. The elemental powders were
sealed into quartz tubes under a dynamic vacuum of 5.5 × 10−4 Pa. The
sealed samples were heated in a muffle furnace from room temperature
to 610 °C with a heating rate of 1 °C min−1. After it was maintained at
610 °C for 168 h, the furnace was cooled to room temperature naturally,
and a series of bulk samples were obtained. High-entropy MPCh3 NSs
were obtained from an ultrasonication-assisted exfoliation technique.
Bulk high-entropy MPCh3 (50 mg) was added to the water−ethanol
solution (100 mL) and ground for 120 min to ensure that large particles
were sufficiently crushed into small ones. The dispersion liquid was
sonicated for 2 h (500 W) at room temperature in an ultrasonic washer.
The mixture was centrifuged and the supernatant was decanted. Then,
the supernatant was put in a typical probe sonicator for 3 h, and the
sonication power was adjusted to 900 W with an on/off cycle of 5/3 s to
get the exfoliated high-entropy MPCh3 NSs. The uniform solution was
centrifuged at 3000 rpm first. Then, the decanted supernatant was
centrifuged again at 9000 rpm, and the high-entropy MPCh3 NSs were
obtained. The samples were washed with absolute ethanol and water
sequentially. Finally, the high-entropy MPCh3 NSs were dried at 60 °C
for 12 h in a vacuum oven.
Synthesis of Pure MPCh3 NSs. The preparation of precursors for
the synthesis of pure MPCh3 (CoPS3, VPS3, MnPS3, NiPS3, and ZnPS3)
followed similar protocols except the amounts of metal powder used
and the holding temperature. The CoPS3 sample was prepared at 550
°C for 720 h. The VPS3 sample was synthesized at 470 °C for 720 h. The
ZnPS3 sample was additionally heated at 750 °C for 168 h. The other
steps were the same as those mentioned above.
Structural Characterization. PXRD measurements were per-
formed on a Rigaku D/max 2500 X-ray diffractometer using Cu Kα
radiation (λ = 1.5406 Å). XPS spectra were recorded on an ESCALAB
MKII spectrometer using an Al Kα excitation source. A JEOL ARM
200F transmission electron microscope and a field-emission gun (FEG)
scanning electron microscope (JEOL 6500 SEM) were used to
characterize the morphology and structure of the NSs. The thickness of
the MPCh3 NSs was analyzed by AFM on a Bruker DI MultiMode-8
system. The ICP-MS analysis was carried out on an Agilent
ICPMS7800 spectrometer.
Electrochemical Measurements. Electrochemical measurements
were performed with a standard three-electrode setup (CH Instru-
ments) using Hg/HgO as the reference electrode, a graphite rod (Alfa
Aesar, 99.9995%) as the counter electrode, and a clean carbon fiber
cloth coated with drop-cast MPCh3 catalysts as the working electrode.
The catalyst was ultrasonically dispersed in a water−ethanol solution
(v/v = 3:7) containing 0.1 wt % Nafion to get the catalyst ink of 5 μg
https://doi.org/10.1021/acsnano.2c01064
ACS Nano 2022, 16, 3593−3603
ACS Nano www.acsnano.org
μL−1, and 70 μL of the catalyst ink was drop-casted onto the carbon
fiber cloth electrode with a geometric area of 1 cm2. The amount of
deposited catalyst was calculated to be ∼350 μg. All the measurements
were performed in a H2-saturated KOH (1.0 M) aqueous solution. CVs
taken at various scan rates (20−80 mV s−1) were collected and used to
extract the double-layer capacitance. The EIS measurements were
carried out at a 100 mV overpotential in the frequency range from 106 to
0.1 Hz. The electrochemical stability of the catalyst was evaluated by
cycling the electrodes for 3000 times. All the potentials were referenced
to a reversible hydrogen electrode (RHE). To extract the Aapp and Eapp
for HER, the electrochemical measurements of the catalysts were
conducted in 1.0 M KOH solution at different temperatures. For the
heterogeneous electrocatalytic reaction, the current density can be
expressed from Eapp in the Arrhenius equation:55
j = A app exp(− Eapp(RT )−1)
(1)
where Aapp is the apparent pre-exponential factor, R is the ideal gas
constant (8.314 J K−1 mol−1), and T is the temperature in Kelvin (K).
Therefore, Eapp can be further calculated from fitting the slope of the
Arrhenius plot using the equation78
|∂(log10 j)∂(1/T )−1|η = − Eapp(2.303R )−1 (2)
while the intercept of log10jvs 1/T plot is the logarithm of Aapp.
THEORETICAL CALCULATIONS
DFT Calculations. All the DFT calculations were performed
by using the CASTEP code.79 All-electron calculations were
employed using the generalized gradient approximation and the
Perdew, Burke, and Ernzerhof functional.80 The ultrasoft
pseudopotentials were used, which are fairly efficient compared
with the norm-conserving pseudopotentials. The plane-wave
cutoff energy was 450 eV, and the Grimme method for DFT-D3
was used to account for van der Waals interactions. The
minimum energies for all structures were obtained until the
energy became less than 2 × 10−5 eV/atom. The vacuum gap
between periodic images was set to 15 Å to avoid interaction.
The Brillouin zone was sampled with a 2 × 2 × 1 gamma-
centered special k point grid for geometry optimization.
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsnano.2c01064.
Figures of a schematic illustration for the synthesis
process; PXRD patterns of high-entropy MPCh3 bulk
samples; PXRD patterns of single-cation MPCh3 bulk
samples; PXRD patterns of bulk Cox(VMnNiZn)1−xPS3;
SEM images of bulk samples; TEM image of CoPS3 NSs;
enlarged (001) peaks for bulk Cox(VMnNiZn)1−xPS3;
Rietveld refinement; electrochemical characterizations;
EIS plots; CV curves; durability test; LSV curves in the
temperature range; logarithm of the catalytic current
density; extraction of Eapp; P 2p and S 2p XPS spectra;
structural characterizations after stability test; crystal
structure and surface-chemical state characterizations
after stability test; HER free-energy diagram; calculated
charge-density difference; tables of reliability factors in
Rietveld refinement; electrocatalytic performance param-
eters; comparison of HER activity; valence-state
proportions; and dissolution ratios (PDF)
3600
Article
AUTHOR INFORMATION
Corresponding Author
Bo Song − National Key Laboratory of Science and Technology
on Advanced Composites in Special Environments, Harbin
Institute of Technology, Harbin 150001, China; orcid.org/
0000-0003-2000-5071; Email: songbo@hit.edu.cn
Authors
Ran Wang − National Key Laboratory of Science and
Technology on Advanced Composites in Special Environments,
Harbin Institute of Technology, Harbin 150001, China;
orcid.org/0000-0002-2034-7189
Jinzhen Huang − National Key Laboratory of Science and
Technology on Advanced Composites in Special Environments,
Harbin Institute of Technology, Harbin 150001, China;
orcid.org/0000-0002-0274-0454
Xinghong Zhang − National Key Laboratory of Science and
Technology on Advanced Composites in Special Environments,
Harbin Institute of Technology, Harbin 150001, China
Jiecai Han − National Key Laboratory of Science and
Technology on Advanced Composites in Special Environments,
Harbin Institute of Technology, Harbin 150001, China
Zhihua Zhang − School of Materials Science and Engineering,
Dalian Jiaotong University, Dalian 116028, China
Tangling Gao − Institute of Petrochemistry, Heilongjiang
Academy of Sciences, Harbin 150040, China
Lingling Xu − Key Laboratory of Photonic and Electronic
Bandgap Materials, Ministry of Education, School of Physics
and Electronic Engineering, Harbin Normal University,
Harbin 150080, China
Shengwei Liu − School of Environmental Science and
Engineering, Guangdong Provincial Key Laboratory of
Environmental Pollution Control and Remediation
Technology, Sun Yat-sen University, Guangzhou 510006,
China; orcid.org/0000-0001-5677-1769
Ping Xu − MIIT Key Laboratory of Critical Materials
Technology for New Energy Conversion and Storage, School of
Chemistry and Chemical Engineering, Harbin Institute of
Technology, Harbin 150001, China; orcid.org/0000-
0002-1516-4986
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsnano.2c01064
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (Grant Nos. 52072085, 52072078, and
51902091).
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