i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 1 1 0 e1 6 1 1 9

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Ultrathin MoSSe alloy nanosheets anchored on

carbon nanotubes as advanced catalysts for
hydrogen evolution

Junhua Qiao a, Fangfang Song a, Jianguo Hu b, Da Huo a, Junhua Yuan a,c,*,

Jianfeng Shen d,**, Li Niu e, Ai-jun Wang a
a
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Life Sciences and
Chemistry, Zhejiang Normal University, Jinhua, Zhejiang, 321004, China
b
Department of Scientific Research Management, Jiangxi University of Traditional Chinese Medicine, Nanchang,
Jiangxi, 330004 China
c
School of Pharmacy, Hubei University of Science and Technology, Xianning, Hubei, 437100, China
d
Center of Special Materials and Technology, Fudan University, Shanghai, 200433, China
e
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy
of Sciences, Changchun, Jilin, 130022, China

article info abstract

Article history: The activity of transition metal dichalcogenides (TMD) toward hydrogen evolution reaction
Received 11 January 2019 (HER) derives from the active sites at the edges, but the basal surface still remain catalytic
Received in revised form insert. Herein, ultrathin MoSSe alloy nanosheets array on multiwalled carbon nanotubes
9 April 2019 (MWCNTs) to form a core shell structure via a simple solvothermal process. These three-
Accepted 24 April 2019 dimensional (3D) MoSSe hybrids show a high activity in hydrogen evolution reaction
Available online 18 May 2019 (HER) with a small Tafel slope of 38 mV dec
1 and a low overpotential of 102 mV at
10 mA cm
2. In addition, their HER activity remains remarkably stable without significant
Keywords: decay after 100 h polarization. Such superior catalytic HER activity springs from the 3D
Hydrogen evolution reaction hierarchical heterostructure, which is abundant of catalytic edge sites, and the alloy effect
Core shell between S and Se, which will create huge defects and strain to form vacancy sites on the
Alloy basal plane. This strategy may open a new avenue toward the development of nonprecious
Nanosheets high-performance HER catalysts.
© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

sustainable energy. Hydrogen fuel is an alternative to fossil

Introduction fuel due to abundance, versatility, carbon-free emission and
high energy density [1]. However, at present, H2 produces via
The depletion of fossil fuel and the deterioration of natural steam reforming process, which will accelerate fossil fuel
environment demand the exploitation of clean and depletion and CO2 emissions [2,3]. Water electrolysis can

* Corresponding author. Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Life Sciences and
Chemistry, Zhejiang Normal University, Jinhua, Zhejiang, 321004, China.
** Corresponding author.
E-mail addresses: jhyuan@zjnu.cn (J. Yuan), jfshen@fudan.edu.cn (J. Shen).
https://doi.org/10.1016/j.ijhydene.2019.04.232
0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 1 1 0 e1 6 1 1 9
supply H2 with a high purity [4]. This sustainable and cost-
effective H2 production can convert ubiquitous H2O into
inexhaustible H2 fuel [5]. Hydrogen evolution is a half-reaction
of water electrolysis, Pt-based catalyst is an ideal catalyst used
in HER because of its high electrochemical activity, long-term
stability and low evolution overpotential, but its scarcity and
expensive price will make water electrolysis economically
infeasible [6,7]. Recent efforts focus on the earth-abundant
transition metals for HER, such as phosphides, chalcogen-
ides, carbides, and nitrides. The HER overpotentials at these
catalysts usually exceed the theoretical minimum limit,
leading to the energy-inefficiency of mass H2 production [8,9].
Layered transition metal dichalcogenides (TMDs), such as
the sulfides and selenides of Mo and W, attract considerable
attention recently as HER catalysts on account of their low
cost, high HER activity and stability [10e12]. These two-
dimensional (2D) materials are similar to graphite, wherein
metal atoms are intercalated to the layer of chalcogenide
atoms in a hexagonal arrangement [13,14]. Current experi-
ments and theoretical simulation confirm that the HER ac-
tivity of the crystalline TMD derives from its edge, rather than
the basal planes [15]. Surface engineering has been exploited
to increase the density of edge sites on the crystalline TMD,
such as lithiation exfoliation [16], hydrogen annealing [17] and
oxygen plasma exposure [18]. These treatments will generate
surface defects in the crystalline TMD at the scale from the
discrete atoms to macroscopic continuum. Nevertheless, the
complicated procedures in surface engineering will limit its
wide application in the scale synthesis of nanostructured
TMD [19]. In comparison, amorphous TMD is intrinsically rich
in the defect sites [20]. Solvothermal strategy is widely used in
synthesis of theses amorphous TMD in large scale with
various nanostructures, including nanowire [21], nanotubes
[22], nanoflakes [23], nanoplates [24] and vertical nanosheet
array [25]. The structural design can make amorphous TMD
full of edge sites and surface defects with 3D architecture. This
3D superstructure will accelerate electron transfer and mass
diffusion [26]. For amorphous MoS2, the HER activity is
assigned to the bridging S2
2 in defect sites. This unsaturated
S-edge can form SeH bonds in acid solution, which may favor
H2 evolution [27]. MoSe2 shares a layered structure close to
MoS2. The unsaturated Se-edges in amorphous MoSe2 are
extremely active as S-edges in MoS2 [28,29]. Theoretical cal-
culations suggest that MoSSe may possess a nearly zero free
energy for H2 adsorption (DGH) at the edge of S-Mo-Se [30]. V.
Kiran et al. indicated that the introduction of Se into the MoS2
lattice may modify the electronic structure and thereby the
DGH. Se doping in the MoS2 lattice may produce defects and
residual strain, which accounts for high HER activity of MoSSe
alloys [31]; Q.F. Gong et al. reported that the optimum Se/S
ratio is 1:1 for MoS2(1
x)Se2x alloy nanoflakes, and their high
HER activity may be ascribed to thermo-neutrality of DGH on
Se-Mo-S edges [23]; Z. Pu et al. demonstrated that Se-doping
can increase the conductivity of MoS2 nanosheet array, and
then enhance its HER activity [32]; Q. Fu et al. suggested that
the introduction of Se into WS2 crystals can induces a slight
distortion on the basal plane, which will lead to the
enhancement of HER activity for monolayer WS2(1e x)Se2x [35].
TMD is a promising alternative to Pt-based HER catalysts,
but the pure TMDs fail to reach the requirement of
16111
commercialization due to the poor conductivity. To further
improve the hydrogen evolution performance, TMDs are rec-
ommended to be deposited on the carbon support [36e38].
Among carbon supports, carbon nanotube (CNT) is a desirable
candidate as support due to its great specific areas, high
electrical conductivity and excellent chemical stability, using
CNTs as carbon support for HER can significantly improve HER
activity [39e42]. Herein, amorphous MoSSe nanosheets were
decorated on CNTs by one-step solvothermal method. Ultra-
thin MoSSe alloy nanosheets can substantially increase active
sites and promote charge transfer. Moreover, the inside car-
bon nanotube can act as a nanocable to improve the con-
ductivity for electron transportation. As expected, the as-
prepared MoSSe/MWCNT hybrids exhibit a superior HER ac-
tivity with a low overpotential, small Tafel slope. This study
can offer a valuable insight into the relationship between TMD
structure and catalytic performance.
Experimental
Synthesis of MoSSe/MWCNT hybrids
In a typical synthesis, 0.15 g MWCNTs (purity>95%, out
diameter 10e20 nm, length~30 mm, purchased from Chengdu
organic Chemics Co., Ltd) was stirred by ultrasound in a co-
solvent of 5 mL deionized water and 15 mL ethanol to form a
MWCNT suspension. In another beaker, 3 mmol S and 3 mmol
Se powder were dissolved in 8 mL of hydrazine solution at
90  C. The mixture solution containing S and Se was slowly
added into the MWCNT suspension, and then a stoichiometric
amount of Na2MoO4 was added to the above solution at a final
Mo:Se:S molar ratio of 1:1:1. The resulting homogeneous
mixture solution is stirred in an ultrasonic bath for 30 min at
room temperature and transferred into a 50 mL Teflon-lined
autoclave and sealed in steel jacket. The autoclave was heat-
ed at 230  C for 10 h, and cooled naturally to room tempera-
ture. The MoSSe/MWCNT hybrids were collected by
centrifugation at 12000 rpm and further purified by washing
with distilled water and ethanol.
For comparison, MoS2/MWCNT and MoSe2/MWCNT hy-
brids were prepared using Se or S powder as precursor. MoS2,
MoSe2 and MoSSe powder was also synthesized without
MWCNTs. The synthetic procedures are similar to those of
MoSSe/MWCNT hybrids.
Material characterization
The morphological observation of the MoSSe/MWCNT hybrids
was performed using transmission electron microscopy (TEM,
JEOL 2010) under an acceleration voltage of 200 kV. The
chemical composition of the MoSSe/MWCNT hybrids was
analyzed using the inductively coupled plasma-atom emis-
sion spectroscopy (ICP-AES, Varian, 700-ES). The crystalline
data of the MoSSe/MWCNT hybrids was characterized by X-
ray powder diffraction (XRD, PANalytical pw 3040/60 X'pert)
with Cu Ka radiation, and further investigated by Raman
spectra (alpha300S, WITec) with 532 nm wavelength laser
excitation under 1 mV power. The chemical state of elemental
composition was determined using X-ray photoelectron
16112 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 1 1 0 e1 6 1 1 9
spectroscopy (XPS, K-alpha, ThermoFisher) with 1486.6eV Al
Ka radiation.
Electrochemical measurements
Electrochemical measurements were performed with a stan-
dard three-electrode setup interfaced to a CHI 750D electro-
chemical workstation (CHI Instruments, Chenhua Co,
Shanghai, China), using a saturated calomel electrode (SCE) as
the reference electrode, and glassy carbon electrode (3 mm in
diameter) coated with the HER catalysts as the working elec-
trode, a graphite rod as the counter electrode. For a typical
preparation of HER catalysts modified electrode, 3 mg of the
catalysts was added into 60 mL of water and ultrasonicated to
form a dark homogeneous suspension. Then a drop of the
catalysts (about 2.5 mL) was transferred onto electrode with
nafion@117 and air-dried at room temperature for the elec-
trochemical measurements. All the measurements were per-
formed in N2-saturated 0.5 M H2SO4 (aq) and the electrode
potentials are calibrated against a reversible hydrogen elec-
trode (RHE): ERHE ¼ ESCEþ0.059 pH þ 0.242 V [43].The HER ac-
tivity was investigated using a linear sweep voltammetry
(LSV) with a scan rate of 5 mV s
1. The iR correction is per-
formed by Ecorr ¼ E-iRu, where Ru is referred to Ohmic resis-
tance arising from the electrolyte/contact resistance of the
setup, measured and compensated by the potentiostat using
the current interrupt method [44,45]. The cyclic voltammetry
(CV) was carried out at the potential range from
Fig. 1 e TEM images of MoS2/MWCNT (A, B, C), MoSSe/MWCNT (D, E, F) and MoSe2/MWCNT hybrids (G, H, I) under different
magnification: (A, D, G) 0.2 mm, (B, E, H) 20 nm, (C, F, I) 5 nm.

0.158e0.342 V vs RHE at various scan rates (5, 10, 20, 40, 60, 80
and 100 mV s
1). The long-term durability was tested by
chronoamperometry (CA) and the electrochemical impedance
spectroscopy (EIS) was obtained at the modulation amplitude
of 5 mV with the frequency range from 105 to 0.01 Hz.
Result and discussion
Morphologic characterization of MoSSe/MWCNT catalysts
The morphology of the typical products was examined by TEM
measurements, as shown in Fig. 1, all molybdenum dichal-
cogenides (MoX1X2, X1, X2 ¼ S, Se) are uniformly anchored on
MWCNT, and presented as curled nanosheets with dense
interconnected ripples (Fig. S1). These MoX1X2 nanosheets
were perpendicularly oriented on MWCNTs without agglom-
eration and stacking. This unique core-shell nanostructure
will favor ion diffusion and efficiently accelerate the electron
transfer [28]. The thickness of MoX1X2 nanosheets can be
estimated by the curve edges of the nanosheets in cross-
section TEM images [29]. The thickness of MoSe2 and MoSSe
is averaged to be 5.8 nm and 3.6 nm, respectively, thicker than
those of MoS2 (1.5 nm), indicating that MoX1X2 in the hybrids
possesses multilayer structure. The interlayer spacing is
estimated to be 0.62 nm for MoS2, 0.65 nm for MoSSe, and
0.68 nm MoSe2, respectively, in good agreement with their
(002) lattice spacing [31,32]. For comparison, pure MoSSe
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 1 1 0 e1 6 1 1 9 16113

nanosheets were synthesized without MWCNT, which are
shown as aggregated structures with wrinkled spherical
configurations (Fig. S2). Fig. 2 reveal the elemental distribution
of the MoSSe/MWCNT hybrids. Obviously, all of Mo, S and Se
elements were uniformly distributed along the MWCNTs,
indicating the formation of the MoSSe alloy nanosheets on
MWCNTs with a core-shell hybrid superstructure. The EDS
curve gave the stoichiometric ratio of 1:1:1 for Mo, S and Se in
MoSSe alloy nanosheets on MWCNTs, in accordance with ICP-
AES results (Table S1).
Fig. 3A shows XRD patterns of MoX1X2/MWCNTs hybrids.
For MoS2/MWCNT hybrids, their XRD pattern indicates that
the diffraction at 2q ¼ 14.4, 39.6, 49.8 and 59.6 are assigned to
(002), (100), (103) and (110) crystal planes of 2H-MoS2,
respectively (JCPDF No 37-1492) [33]. After Se doping, the cor-
responding diffraction peaks move to 2q ¼ 14.0, 32.1, 38.6 and
58.0 , which match the (002), (100), (103), and (110) crystal
planes of MoSSe (JCPDS No. 36-1408). For MoSe2/MWCNT hy-
brids, their four main peaks at 13.7, 37.8, 47.5 and 57.5 are
assigned to (002), (100), (103) and (110) crystal planes of 2H-
MoSe2 [31,34]. Obviously, Se doping in MoS2 nanosheets will
lead to a red-shift of the diffraction peaks, which is consistent
with the expansion of unit cells upon the substitution of sulfur
atoms with larger selenium atoms [23]. Fig. 3B shows the
Raman spectra of MoX1X2/MWCNTs hybrids under 514 nm
laser excitations. For MoS2 nanosheets, the in-plane E2g vi-
brations occur at 382 cm
1, and the out-of-plane A1g vibration
at 403 cm
1 [23]. The large E2g/A1g intensity ratio indicates

Fig. 2 e TEM-EDS mappings of MoSSe/MWCNT hybrids. (A) TEM image, scale: 0.2 mm, the corresponding element
distribution: (B) Mo, (C) S, (D) Se and (E) their EDS curve.
16114 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 1 1 0 e1 6 1 1 9
Fig. 3 e XRD pattern (A), Raman spectra (B) of MoX1X2/MWCNT hybrids and XPS of Mo-3d (C) and S-2p regions (D)
corresponding to MoX1X2/MWCNT hybrids.
abundant edges of MoS2 nanosheets [46]. For MoSe2 nano-
sheets, the Raman spectrum is emerged at 237 and 286 cm
1,
corresponding to A1g and E2g vibration modes of MoSe2,
respectively [47,48]. The Raman spectrum of MoSe2 shows a
red shift compared to the MoSe2 bulk materials indicating the
presence of single or few layer structures [49]. For MoSSe
nanosheets, Se introduction will soften Mo-S bond, leading to
a blue shift of the E2g and A1g vibration of Mo-S related mode
[50]. Meanwhile, Mo-Se vibration will appear and highlight.
Such features in Roman spectra reveal an alloying of MoSSe
nanosheets at the molecular level [30].
The chemical states of Mo, S and Se in MoX1X2/MWCNTs
hybrids were determined by XPS. The deconvolution of Mo 3d
spectra in Fig. 3C shows two valence state of Mo element: Mo
(IV) and Mo (VI). Further data fitting reveals the presence of 1T
and 2H phase in Mo (IV) components. The 1T phase of Mo (IV)
component is dominant in MoX1X2 nanosheets. Its fraction is
determined by integrating the XPS areal of Mo (IV) doublets,
which is 76% for MoS2, 70% for MoSSe and 72% for MoSe2,
respectively. For MoS2/MWCNT hybrids, Mo (IV) doublets at
228.6 and 231.7 eV are assigned to 1T phase of Mo (IV) 3d 5/2
and 3/2 orbitals, respectively, whereas another Mo (IV) dou-
blets at 229.7 and 232.2 eV corresponds to the 2H phase of Mo
(IV) 3d 5/2 and 3/2 orbitals, respectively [51,52]. Se introduction
will cause a negative shift of the binding energy for 2H-Mo (IV)
3d 5/2 from 228.6 (MoS2) to 228.3 eV (MoSSe). This result
demonstrates that Se introduction can modify significantly
the electronic structure of Mo (IV) 3d doublets in MoS2 [23,31].
Besides, another pair of Mo peaks can be observed at about
232.2 and 235.4 eV, which are identified as Mo (VI) 3d 5/2 and
3d 3/2 orbitals, respectively [36,53]. In addition to Mo signal, S
2s orbital is presented at about 226.0 eV for both MoS2 and
MoSSe [31]. For MoSSe, S 2p orbitals are presented at 161.6 (S
2p 3/2), and 163.1 eV (S 2p 1/2), and Se 2p orbitals at 160.4 (Se 2p
3/2) and 166.8 eV (Se 2p 1/2) [31] (Fig. 3D). S 2p signal shifts
negatively by 0.4 eV when compared with that of MoS2, and Se
2p signal moves positively by 0.3 eV in contrast with that of
MoSe2, which is in good agreement with the variation on the
binding energy for Mo (IV) doublets in MoS2 after Se
introduction.
The HER activity of MoX1X2/MWCNT catalysts was inves-
tigated by LSV in a N2-saturated 0.5 M H2SO4 solution. The
performances of pure MoX1X2, MWCNTs and Pt/C catalysts
were measured as comparisons. Fig. 4A show their iR-
corrected LSV curves of HER catalysts modified electrodes.
The MoX1X2/MWCNT catalysts exhibit smaller onset over-
potentials by comparison with pure MoX1X2, indicating that
MWCNT introduction can improve HER activity. The onset
overpotential of MoSSe/MWCNT electrode is
25 mV at
0.1 mA cm
2, a lowest potential apart from commercial Pt/C
among HER catalysts, suggesting a superior catalytic HER ac-
tivity. Tafel plots are widely used in quantitative kinetic
analysis of HER. The superior HER activity of MoSSe/MWCNT
electrode is also reflected in its low Tafel slope. As shown in
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 1 1 0 e1 6 1 1 9 16115

Fig. 4 e (A) iR-corrected LSV curves of HER catalysts in 0.5 M H2SO4 solution at the scan rate of 5 mV s¡1. (B) The
corresponding Tafel slope. (C, D) The comparison between overpotential required at 10 mA cm¡2 (C) and exchange current
density (D). (E) The capacitive current plotted against scan rates of the HER catalysts. (F) The Nyquist plots of the HER
catalysts at overpotential of 100 mV.

Fig. 4B, the sequence of Tafel slope at 10 mA cm
2 for the HER
catalysts follow the order of decrease: MoSe2 (202 mV dec
1),
MoS2 (143 mV dec
1), MoSSe (102 mV dec
1), MoSe2/MWCNT
(61 mV dec
1), MoS2/MWCNT (47 mV dec
1), MoSSe/MWCNT
(38 mV dec
1) and Pt/C (30 mV dec
1). For MoSSe/MWCNT
electrode, the smaller Tafel slope is beneficial to water split-
ting as it suggests a faster kinetics of HER. Specially, the Tafel
slope of MoSSe/MWCNT hybrids is close to the theoretical
value of 40 mV dec
1 when the Volmer-Heyrovsky reaction
pathway is operative with electrochemical desorption of
hydrogen as the rate-limiting step [23]. The superior HER ac-
tivity of MoSSe/MWCNT electrode is also embodied in the
smaller overpotential (h) acquired at 10 mA cm
2. As shown in
Fig. 4C, the HER overpotential is 102 mV for MoSSe/MWCNT
electrode, only above Pt/C catalysts (30 mV), but lower than
those of MoX1X2/MWCNT counterpart (MoS2/MWCNT 172 mV
and MoSe2/MWCNT 232 mV) and pure MoX1X2 (MoSSe 262 mV,
MoS2 305 mV and MoSe2 396 mV). The exchange current
density (Jo) is another important parameter of HER activity,
which can be deduced by extrapolating Tafel plots to 0 mV
(Fig. 4D) [54]. MoSSe/MWCNT electrodes show a Jo value of
1.39 mA cm
2, lower than that of Pt/C (2.88 mA cm
2), but
largest among MoX1X2/MWCNT and pure MoX1X2, indicative
of an intrinsically faster HER kinetics. The Tafel slope and h at
16116 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 1 1 0 e1 6 1 1 9

10 mA cm
2 were charted in Table 1. The superior HER activity
of MoSSe/MWCNT catalyst is better than or comparable to
those of metal chalcogenide reported recently [23,55e63].
The superior HER activity of MoSSe/MWCNT hybrids can be
attributed to the hierarchical hybrid structure and the alloying
effect between S and Se atom. The direct growth of MoSSe
nanosheets on MWCNTs can enhance the intrinsic conduc-
tivity of MoSSe, resulting in an even higher electrochemical
active surface area (ECSA). The ECSA value of the catalyst can
be calculated by dividing the double-layer capacitance (Cdl)
with the specific capacitance (Cs) of the sample as follows [64].
Cdl
ECSA ¼
Cs
Cdl value was measured by cyclic voltammetry (CV) in the
non-faradaic region (Fig. S3). Fig. 4E plotted the capacitive
current against the scan rate. The Cdl value of MoSSe/MWCNT
electrode is 4.62 mF cm
2. The specific capacitance for a flat
surface is based on typical values reported for metal elec-
trodes in aqueous H2SO4 and NaOH solutions [65]. Herein, the
specific capacitance is 0.035 mF cm
2 in 0.5 M H2SO4. The h, b,
Cdl and ECSA value of as-prepared HER catalysts was listed in
Table S2. The ECSA value of MoSSe/MWCNT electrode is
calculated to be 1320 cm2, larger than that of MoS2/MWCNT
(932 cm2) and MoSe2/MWCNT (868 cm2) MoX1X2/MWCNT
counterparts. On the other hand, The MoX1X2/MWCNT elec-
trodes show a larger Cdl and ECSA value than those of MoX1X2
electrodes. Thus, MWCNT introduction will increase conduc-
tivity of TMD [66], which will favor electron transfer along
MWCNTs. The high ECSA value of MoSSe/MWCNT electrode
will help in improving the HER activity. The specific activity (Js)
can be obtained by normalizing the current density by the
ECSA value of the catalysts (Fig. S4). The sequence of specific
activity at 100 mV vs RHE for the HER catalysts follows the
order of decrease: MoSSe/MWCNT (5.98 mA cm
2), MoSSe
(2.23 mA cm
2), MoSe2/MWCNT (0.86 mA cm
2), MoSe2
(0.38 mA cm
2), MoS2/MWCNT (0.08 mA cm
2) and MoS2
(0.02 mA cm
2). It is clear that pure MoSSe and MoSSe hybrids
show a higher intrinsic activity than those of pure MoX2 and
MoX2 hybrids (X ¼ Se or S). The high specific activity of MoSSe
can be associated with the alloying effect in MoSSe nano-
sheets. As revealed by XPS analysis, the alloying effect in
MoSSe modifies the electronic structure of Se and S atoms,
and moves the H adsorption energy toward thermos-
neutrality, leading to a decrease in HER overpotential [23,30].
In addition, the presence of S/Se in the MoSSe lattice may
introduce defects and residual strain due to mismatch of size
mismatch between S and Se atom. Therefore, Se (or S) doping
will create catalytically vacancy sites on its basal plane be-
sides the edge sites, which may account for the high HER ac-
tivity of MoSSe alloy nanosheets [31,35].
The electrode kinetics was investigated by EIS under HER
process. As shown in Fig. 4F, the X-intercept of the Nyquist
curves at the high frequency is the definition of the equivalent
series resistance (Rs). Herein, the Rs difference mainly derived
from the conductivity of HER catalysts on the electrode [62].
The MoX1X2/MWCNT electrodes show a smaller Rs value than
those of MoX1X2 electrodes due to the introduction of
MWCNTs, which can act as collector to conduct electrons. On
the other hand, the Nyquist plots are presented as a semicircle
at
10 mV vs RHE, which revealed a dramatically decreased
charge transfer resistance (Rct) [62]. The MoSSe/MWCNT
electrode shows a smallest Rct value of 12 U amongst the
MoX1X2/MWCNT hybrids, its Rct value is far below that of pure
MoSSe (173 U). The smaller Rct value of MoSSe/MWCNT elec-
trode is associated with its core-shell structure and the
alloying effect in MoSSe, which can provide numerous
exposed active edges and vacancy sites on its basal plane for
the electron transfer as well as shortened pathways for mass
transport, leading to an enhanced HER activity [63].
Stability is also a requisite parameter as advanced HER
electrocatalysts in practical application. Fig. 5A shows CA
curve of as-prepared HER catalysts at the overpotential of
150 mV. The current fluctuation of Pt/C, MoS2/MWCNT,
MoSe2/MWCNT and MoSSe/MWCNT electrodes indicates the
processes of H2 production and release [67]. Despite these
fluctuation, the HER current of MoSSe/MWCNT electrode
remain 45 mA cm
2 after 1 h polarization at 150 mV vs RHE,
while the HER current of the pure MoSSe decreased continu-
ally from 7.87 to 3.83 mA cm
2. Fig. 5B shows the iR-corrected
LSV curves of as-prepared HER catalysts before and after the
durability test. The LSV curves of MoSSe/MWCNT electrodes
remain almost unchanged after the durability test, while
other HER catalysts, such as MoS2, MoSe2, MoSSe, MoS2/

Table 1 e Comparison of HER performance (h overpotntial and b Tafel slope) at 10 mA cm¡2 in 0.5 M H2SO4 solution for
MoSSe/MWCNT hybrids with TMD HER catalysts reported recently.
Catalyst Composition, Loading Preparation Method h (mV) Tafel slope Ref
(mV dec-1)
MoS2(1-x)Se2x (0.28 mg cm
2) MoCl5 reacts with S/Se powder in the mixture 150 40 [23]
oleylamine and 1-octadecene at 300  C
1T-MoS2/SWNT MoCl5 reacts with TAA on SWCNT film 108 36 [55]
DBC-MoS2-PANI2 MoS2 exfoliated and mixed with PANI-DBC 196 58 [56]
MoS2/g-C3N4 (NH4)6Mo7O24∙4H2O react with urea on C3N4 260 63 [57]
MoS2/RGO (2.5%) (14.1 mg cm
2) (NH4)2MoS4 decomposed on GO 218 57 [58]
1T-MoSe2 (0.14 mg cm
2) Na2MoO4 and Se powder react with NaBH4 152 52 [59]
MoSe2/Graphene MoCl5 reacts with S/Se powder on graphene 159 61 [60]
1T/2HeMoS2 Na2MoO4 reacts with TAA 220 61 [61]
MoSe2 nanosheets MoSe2 exfoliated in the mixture of IPA and H2O2. 150 80 [62]
MoS2@SWNT (NH4)2MoS4 decomposed on SWCNTs 150 41 [63]
MoSSe/MWCNT (0.12 mg cm
2) Na2MoO4 and S/Se powder react with NaBH4 on MWCNTs 102 38 This work
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 6 1 1 0 e1 6 1 1 9
Fig. 5 e (A) the CA curves of Pt/C, MoS2, MoSe2, MoSSe, MoS2/MWCNT, MoSe2/MWCNT and MoSSe/MWCNT electrode at
150 mV vs RHE over 1 h. (B) iR-corrected LSV curves of MoS2, MoSe2, MoSSe, MoS2/MWCNT, MoSe2/MWCNT and MoSSe/
MWCNT electrode at a scan rate of 5 mV s¡1 before (solid line) and after (dash line) durability test.
MWCNT and MoSe2/MWCNT electrodes, suffer from a signif-
icant loss of HER activity with an observable negative poten-
tial shift at 20 mA cm
2. The durability test of MoSSe/MWCNT
electrode extended to 100 h at the overpotential of 150 mV, the
CA curves of MoSSe/MWCNT electrode shows a slow HER
current attenuation from 45 mA cm
2 at 1 h to 34 mA cm
2 at
100 h. The Tafel slope of MoSSe/MWCNT electrode increases
from 38 mV dec
1 before durability to 44 mV dec
1 after
durability. The small variation on HER activity for MoSSe/
MWCNT electrode further confirm a favorable long-term sta-
bility (Fig. S5).
Conclusions
A facile solvothermal strategy was developed to prepare ul-
trathin MoSSe alloy nanosheets arrayed on MWCNTs. This 3D
core-shell heterostructure exhibits a high HER activity with a
small Tafel slope of 38 mV dec
1 and a low overpotential of
102 mV at 10 mA cm
2. Moreover, their HER activity remains
remarkably stable without significant decay after 100 h po-
larization. The superior HER performance is associated with
their 3D hierarchical structure, which can enhance the
intrinsic conductivity of MoSSe, resulting in a higher ECSA
value and fast electron transfer. On the other hand, the alloy
effects may introduce defects and residual strains on the basal
plane of MoSSe nanosheets besides the edge sites, leading to
abundant catalytically vacancy sites. Rational design and
controllable synthesis of HER catalysts of TMD with a high
HER activity and stability is still challenge in the hydrogen
economy. Our works provide a fast and cost-effective strategy
to prepare advanced HER catalysts with 3D core-shell heter-
ostructure. Their superior HER activity promises their wide
application in the large-scale H2 production by water splitting,
including energy storage, catalysis, solar thermal energy
harvesting and harsh environment monitoring [68].
Acknowledgement
This work was financially supported by the Natural Science
Foundation of Zhejiang Province (No. LY17B030002).
16117
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2019.04.232.
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