FULL PAPER
Hydrogen Evolution Reaction
Activating MoS2 Basal Plane with Ni2P Nanoparticles
for Pt-Like Hydrogen Evolution Reaction in Acidic Media
Minkyung Kim, Mohsin Ali Raza Anjum, Minhee Lee, Byeong Jun Lee, and Jae Sung Lee*
2D molybdenum disulfide (MoS2) displays a modest hydrogen evolution
reaction (HER) activity in acidic media because the active sites are limited
to a small number of edge sites with broader basal planes remaining mostly
inert. Here, it is reported that the MoS2 basal planes could be activated by
growing nickel phosphide (Ni2P) nanoparticles on them. Thus a Ni2P/MoS2
heterostructure is constructed via in situ phosphidation of an indigenously
synthesized NiMoS4 salt as a single precursor to form a widely cross-doped
and chemically connected heterostructure. The conductivity and stability of
the Ni2P/MoS2 heterostructure are further enhanced by hybridization with
conductive N-doped carbon supports. As a result, the Ni2P/MoS2/N:RGO
or Ni2P/MoS2/N:CNT electrocatalyst displays Pt-like HER performance in
acidic media, outperforming the incumbent best HER electrocatalyst, Pt/C,
in a more meaningful high current density region (>200 mA cm−2) making
them a promising candidate for practical water electrolysis applications.
Since nonprecious metal catalysts showing Pt-like HER performance in
acidic media are rare, the Ni2P/MoS2 heterostructure catalyst is a promising
candidate for practical hydrogen production via water electrolysis.
1. Introduction
The hydrogen production via electrochemical water splitting
combined with a renewable power generation is a sustainable
way to address both energy and environmental issues of the
world.[1] The noble metals (Pt, Ru) are most efficient hydrogen
evolution reaction (HER) catalysts in acidic electrolyte, but
a cheaper nonprecious metal electrocatalyst is desired for
practical large scale applications.[2] A large number of transition
metal compounds have been extensively studied as nonprecious
metal HER electrocatalysts such as transition metal
phosphides,[3] chalcogenides,[1,4] carbides,[1,5] and nitrides.[1,5a]
Molybdenum disulfide (MoS2) has received great attention as
a pH-universal electrocatalyst,[6] yet its HER activity is modest
because active catalytic sites are limited to the small number
M. K. Kim, Dr. M. A. R. Anjum,[+] M. H. Lee, B. J. Lee, Prof. J. S. Lee
School of Energy and Chemical Engineering
Ulsan National Institute of Science and Technology (UNIST)
50 UNIST-gil, Ulsan 44919, South Korea
E-mail: jlee1234@unist.ac.kr
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.201809151.
[+]
Present address: Chemistry Division, Directorate of Science, Pakistan
Institute of Nuclear Science and Technology (PINSTECH), Nilore,
Islamabad 45650, Pakistan
DOI: 10.1002/adfm.201809151
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www.afm-journal.de
of edge sites while broader basal planes of
MoS2 remain inert.[4b,7] Numerous efforts
have been devoted to enhancing the HER
activity of MoS2 through maximizing the
number of exposed active sites,[6,8] gen-
erating sulfur vacancies and defects,[6,9]
doping with heteroatoms,[10] assembling
with conductive carbon materials,[11]
and controlling the phase.[12] Despite all
of these efforts, increasing the catalytic
activity of MoS2-based electrocatalysts on
a par with commercial Pt catalysts still
remains a great challenge.[13]
Nickel phosphide (Ni2P) is another
effective HER catalyst that has received
much attention in the past decade owing
to relatively high chemical stability
and electrical conductivity compared to
transition metal carbides, nitrides, and
borides.[1] However, inserting electron-
egative phosphorous (P) into the lattice
of Ni metal restricts the electron delo-
calization, resulting in semiconducting
nickel phosphides.[3a] To enhance the conductivity and intrinsic
catalytic activity of transition metal phosphides, compounding
or solid solution formation with other p-block elements such
as NiPS3,[14] Ni5P4|S,[15] MoP|S,[16] and MoP/SN[17] has been
proposed. Similarly, assembling a phosphide with a sulfide to
make a hybrid catalyst is another attractive approach to enhance
their HER performances. To this end, a few hybrid elec-
trocatalysts have been reported including NiFeSP/Ni foam,[18]
Co3S4/MoS2/Ni2P/C,[19] Co3S4/CoP,[20] and Ni2P/MoO2/
MoS2.[21] Although these electrocatalysts displayed improved
HER activity, they were still far inferior to incumbent Pt/C.
Herein we propose a strategy to increase the activity of MoS2
by forming a Ni2P/MoS2 heterostructure to activate the basal
planes of MoS2 with Ni2P nanoparticles (NPs). The Ni2P NPs are
grown on MoS2 nanosheets by in situ phosphidation of indige-
nously produced NiMoS4 as a single precursor. The Ni2P/MoS2
heterostructure displays an HER activity much higher than
those of individual MoS2 and Ni2P components. Hybridization
of Ni2P/MoS2 with a conductive carbon substrate like N-doped
graphene (Ni2P/MoS2/N:RGO) or N-doped carbon nanotube
(Ni2P/MoS2/N:CNT) further boosts HER performance with
small onset potentials resembling those of Pt/C. In particular,
our hybrid electrocatalysts outperform the other transition
metal-based electrocatalysts and especially Pt/C in high current
density region (>200 mA cm−2). This improved performance
is related to activating the basal plane of MoS2 by forming a
widely cross-doped and chemically connected heterostructure
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with Ni2P nanoparticles. There are several reports of nonpre-
cious metal-based electrocatalysts showing Pt-like HER activity
in alkaline media, but they are rare in “acidic” media. Hence,
the high HER activity and durability of our Ni2P/MoS2/N:RGO
or Ni2P/MoS2/N:CNT catalysts in acidic media suggest their
high potential to replace expensive Pt-based electrocatalysts in
practical water electrolyzers.
2. Results
2.1. Structure and Properties of Ni2P/MoS2 Heterostructures
To promote the strong interaction between Ni2P and MoS2 phases,
their heterostructure was synthesized from a single precursor
NiMoS4. The precursor was synthesized via a cation displace-
ment reaction between (NH4)2MoS4 and Ni(CH3CO2)2·4H2O as
described in the Experimental Section. The NiMoS4 salt reacted
with in situ produced phosphine (PH3) gas from NaH2PO2·H2O
decomposition at a preoptimized temperature of 500 °C for 2 h
to produce the Ni2P/MoS2 heterostructure. To make the Ni2P/
MoS2/N:RGO and Ni2P/MoS2/N:CNT hybrid catalysts, an exfoli-
ated N-doped reduced graphene (N:RGO) or N:CNT was directly
introduced in the NiMoS4 formation step before the in situ
phosphidation reaction as illustrated in Scheme 1.
Thermogravimetric analysis (TGA) curves in Figure  1a
reveal the decomposition process of (NH4)2MoS4. Following the
initial evaporation of water up to 100 °C, MoS3 is formed by
loss of NH3 and H2S molecules until 240 °C. The phase trans-
formation from MoS3 to MoS2 is observed up to 450 °C with
further loss of H2S gas.[6] Similarly, phosphine gas is generated
by thermal decomposition of NaH2PO2·H2O at ≈250  °C.[22]
Therefore, 450–550 °C is the optimized temperature window
for proper phosphidation of the NiMoS4 precursor to form a
Ni2P/MoS2 heterostructure. The X-ray diffraction (XRD) pattern
of Ni2P/MoS2/N:CNT hybrid catalyst in Figure 1b confirms
formation of the two phases, MoS2 and hexagonal Ni2P (space
group: P-62m). Interestingly, the (002) peak of MoS2 displays
an enlarged interlayer spacing (0.68 nm) than the standard
Scheme 1.  Schematic illustration of Ni2P nanoparticles anchored on MoS2 sheets supported on N-doped carbon nanotubes (N:CNT). The NiMoS4
anchored on N-doped CNT reacts with in situ produced PH3 gas to form Ni2P/MoS2/N:CNT heterostructure.
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(0.615 nm), indicating insertion of some heteroatoms (P, or
Ni) between two MoS2 layers of the Ni2P/MoS2 heterostruc-
ture. The XRD patterns of Ni2P/MoS2-X (X  = 450–550 °C)
heterostructures synthesized at different annealing tempera-
tures in Figure S1 of the Supporting Information indicate that
a bimetallic phosphide (MoNiP2) phase is dominating when the
temperature rises above 500 °C, instead of the heterostructure.
The surface morphology of Ni2P/MoS2/N:CNT was deter-
mined by scanning electron microscopy (SEM) as shown in
Figure 1c, which confirms the successful hybridization of all
these three components into a porous hybrid structure. The
SEM images of MoS2, Ni2P, Ni2P/MoS2, and Ni2P/MoS2/N:RGO
are also displayed in Figures S2–S4 (Supporting Information).
The Raman spectra in Figure 1d give further information about
the structural evolution of MoS2 upon forming heterostructure
and hybrid. Thus, the peaks at 379.5 and 407.3 cm−1 are attrib-
1
uted to E 2g and A1g vibrational modes of MoS2, respectively. The
1
redshift of E 2g (378.5 cm−1) and A1g (401.4 cm−1) of Ni2P/MoS2
can be ascribed to the decreased number of MoS2 layers due to
presence of Ni and P species in the heterostructure.[23] Some
weak signals between 250 and 300 cm−1 in Ni2P/MoS2 display
the defective features in MoS2.[6,24] Additionally, the high D
(1345 cm−1) and G (1596 cm−1) band intensities ratio (ID/IG)
in both Ni2P/MoS2/N:RGO (1.03) and Ni2P/MoS2/N:CNT
(1.14) reveal the defective nature of graphitic carbon due to the
presence of N and S dopants.[25]
The nature of chemical bonding in Ni2P/MoS2 was further
investigated by the high-resolution X-ray photoelectron spec-
troscopy (XPS). A doublet at 227.9 and 231.2 eV in the Mo 3d
spectrum in Figure 1e is assigned to a low oxidation state of
Moδ+ (0 < δ ≤ 4) attached to S and/or P to make SMoP type
bonding in Ni2P/MoS2 hybrid.[17] Another doublet at 228.9
and 232.3 eV for Mo4+ 3d5/2 and Mo4+ 3d3/2 demonstrates
the characteristics of MoS2.[16] Two weak signals at 232.3 and
235.0 eV represent the surface oxidation of Mo species to form
MoO3.[17,26] Similarly, a doublet in Ni 2p XPS spectra at binding
energies of 853.0 and 870.3 eV in Figure 1f is ascribed to Ni3+
oxidation states in Ni2P. The peaks at 854.3 and 857.2 eV along
with satellites (862.5 and 875.1 eV) in Ni 2p spectrum are
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Figure 1.  Formation and structural analysis of a Ni2P/MoS2 heterostructure. a) Thermogravimetric analysis (TGA) of (NH4)2MoS4 in air and nitrogen.
b) XRD pattern of MoS2, Ni2P, and Ni2P/MoS2/N:CNT. c) SEM image of Ni2P/MoS2/N:CNT. d) Raman spectra for MoS2, Ni2P/MoS2, Ni2P/MoS2/
N:RGO, and Ni2P/MoS2/N:CNT. High-resolution XPS spectra for e) Mo 3d and f) Ni 2p of Ni2P/MoS2.

attributed to Ni bonded to S and O atoms in the form of sulfides
or surface oxides/hydroxides.[3d,27] Two doublets in P 2p (129.4,
130.2 eV) and S 2p (161.9, 163.0 eV) further confirm the for-
mation of metal phosphosulfides in the material as displayed
in Figure S5 (Supporting Information). The characteristic sig-
nals of CS/NS, SO4 in S 2p,[17] PN/PON, PS,
PC in P 2p,[17] pyridinic, pyrrolic, graphitic nitrogen in N
1s, and CN/N in C 1s spectra confirm that all elements are
chemically interconnected with each other in both Ni2P/MoS2/
N:CNT and Ni2P/MoS2/N:RGO as shown in Figures S6 and S7
(Supporting Information). In Ni2P, doping of a more elec-
tronegative element like S stabilizes the least stable P3− state
in phosphides by withdrawing the electron density from it and
then donates back to vacant d orbitals of Ni.[17] Additionally, the
doping of heteroatoms (N, S, P, and O) in the heterostructure is
known to increase the number of proton (H+) adsorption sites
to improve the HER performance.[17,28]
High-resolution transmission electron microscopy (HR-
TEM) image of Ni2P/MoS2 heterostructure in Figure  2a
shows that Ni2P NPs are successfully grown on MoS2 sheets.
The HR-TEM images (Figure 2b–d) clearly show both Ni2P
and MoS2 phases. Interestingly, stacking of MoS2 sheets is
restricted to only three to seven layers with enhanced inter-
layer spacing (≈0.68 nm) due to presence of Ni and P species
as suggested by XRD and Raman analyses. Thus, Ni2P NPs
residing on the flat basal plane of MoS2 suppress the further
growth of the MoS2 layers. The particle size of Ni2P lies in the
range of 8–15 nm as confirmed by TEM images of Ni2P/MoS2/
N:CNT hybrid catalyst in Figure 2e,f, which also clearly shows
co-existence of Ni2P, MoS2, and CNT. The lattice fringes 0.22,
0.20, and 0.25 nm correspond to (111), (201), and (200) planes of
Ni2P (Figure 2d,g) and enlarged d-spacing (0.68 nm) is for MoS2
(002) plane (Figure 2c,h). The energy-dispersive X-ray spectros-
copy (EDS) SEM elemental mappings confirm the uniform
elemental distribution throughout the particles in Ni2P/MoS2/
N:RGO (Figure S8, Supporting Information) and Ni2P/MoS2/
N:CNT (Figure S9, Supporting Information). The EDS-TEM
element maps and spectrum further confirm that all elements
are well dispersed at atomic levels in Ni2P/MoS2 (Figure S10,
Supporting Information), Ni2P/MoS2/N:CNT (Figure S11, Sup-
porting Information), and Ni2P/MoS2/N:RGO (Figure S12, Sup-
porting Information).
2.2. Electrochemical HER Performance
The HER performances of all synthesized electrocatalysts were
evaluated in 0.5 m H2SO4 aqueous solutions in a three-electrode
cell with Ag/AgCl (3.0 m NaCl) electrode and a graphite rod used
as reference and counter electrodes, respectively. In Figure  3a
and Figure S13 (Supporting Information), it is observed that a
physical mixture of (Ni2P+MoS2) displays lower overpotentials
η1 ≈ 164.6 mV and η10 ≈ 273.6 mV required to generate 1 and
10 mA cm−2 than those of bare Ni2P (174.5 and 374 mV) and
MoS2 (220.9 and 364 mV), showing a synergistic effect between
the two phases. The synergistic effect is further enhanced when
they are closely connected by chemical bonding in the form
of Ni2P/MoS2 heterostructure. Thus, the η1 and η10 values for
Ni2P/MoS2 are further lowered to 23.9 and 91.5 mV, respec-
tively. In Figure S14 (Supporting Information), the highest

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Figure 2.  High-resolution trasmission electron microscopy (HR-TEM) images of Ni2P/MoS2 heterostructure. a) TEM image, b) HR-TEM image, magni-
fied image of c) MoS2 region, d) Ni2P (111) surface, corresponding line profile, and fast Fourier transforms (FFT) for Ni2P/MoS2 catalyst. e) TEM image
showing the Ni2P NPs distributed on MoS2 and CNT, and magnified image (inset) displaying MoS2, Ni2P, and CNTs together. f) HR-TEM image, mag-
nified image of g) Ni2P NPs, h) a few layered MoS2 with enhanced interlayer distance, and corresponding FFTs for Ni2P/MoS2/N:CNT hybrid catalyst.

HER performance is observed for Ni2P/MoS2 electrocatalyst
prepared at 500 °C, where crystalline phases of MoS2 and Ni2P
are formed without sintering or formation of the intermetallic
MoNiP2 phase. The result is significant because the formation
of solid solution has been proposed as an effective method to
improve the HER activity of MoS2.[26,28] The close connection
between the two phases is possible because they are synthe-
sized from the same precursor NiMoS4 containing both metal
atoms.
The HER activity of Ni2P/MoS2 was further enhanced
by anchoring it on highly conductive and porous N:RGO or
N:CNT substrates. Evidently, the carbon supports improve the
electronic conductivity, hinder the aggregation of Ni2P nano-
particles, and prevent stacking of MoS2 layers as confirmed
in HR-TEM in Figure 2. Therefore, the hybrid electrocatalysts
Ni2P/MoS2/N:RGO and Ni2P/MoS2/N:CNT require much
lower η1 (6.79, 27.9 mV) and η10 (39.5, 93.9 mV), respectively.
Especially, the η10 value for Ni2P/MoS2/N:RGO (39.5 mV) is
close to commercial 20 wt% Pt/C (13.4 mV). In particular, both
Ni2P/MoS2/N:RGO and Ni2P/MoS2/N:CNT electrocatalysts
demonstrate even superior performance to that of Pt/C at prac-
tically more important high current densities (>200 mA cm−2).
The Tafel slopes and exchange currents at zero voltage (J0)
are important parameters to determine reaction mechanism
and intrinsic kinetics for HER. Thus, Tafel analysis was per-
formed by using the Tafel equation (η = b × log (j) + a, where
j = current density and b = Tafel slope) as displayed in Figure 3b.
The Tafel slopes and exchange current densities of Ni2P/MoS2/
N:RGO (39.52 mV dec−1 and 0.93 mA cm−2) are comparable to
Pt/C (31 mV dec−1 and 3.46 mA cm−2), and the Tafel slopes sug-
gest that the catalysts follow the Volmer–Heyrovsky mechanism
for HER in acids. The η10 and J0 values for all catalysts are also
compared in Figure 3c. The lowest η10 value of Ni2P/MoS2/
N:RGO relative to previously reported state-of-the-art catalysts
in Figure S15 (Supporting Information) derived from Table S1
of the Supporting Information demonstrates that our hetero-
structured hybrid catalysts are unique in showing Pt-like HER
activity in acidic media.
The number of active sites and turnover frequencies
(TOFs) were also estimated according to a previously reported
method described in the Methods section of the Supporting
Information.[6] Thus the number of exposed metal ion sites
for each electrocatalyst was titrated from integrated charge of
anodic cyclic voltammetry (CV) curve for the whole potential
range in Figure S16 (Supporting Information) measured in
0.1 m phosphate buffer solution (pH 7). Then TOF was calcu-
lated by normalizing the HER current with the titrated active
sites according to the procedure. As in Figure 3d, the number

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Figure 3.  HER performance and stability of Ni2P/MoS2 heterostructures in 0.5 m H2SO4. a) iR-corrected polarization curves for HER. b) Tafel slopes.
c) η10 values (left) and exchange currents (right). d) The number of active sites (left) and TOF at 150 mV (right). e) EIS Nyquist plots (solid line:
fitted; dots: experimental) measured at an overpotential of 100 mV and corresponding equivalent circuit model (inset). f) LSV curves before (solid)
and after (dotted) 3000 CV cycles for Ni2P/MoS2/N:CNT and Ni2P/MoS2/N:RGO. A long-term durability of Ni2P/MoS2/N:CNT determined by
chronoamperometry (CA) at overpotential of 150 mV for 60 h in 0.5 m H2SO4 aqueous solution (inset).

of active sites and the activity per site (TOF) at 150 mV of Ni2P/
MoS2/N:RGO (1.14 × 10−8 mol, 12.27 s−1) and Ni2P/MoS2/
NCNT (1.22 × 10−8 mol, 5.37 s−1) are much higher than those
of Ni2P (5.45 × 10−9 mol, 0.13 s−1), MoS2 (1.27 × 10−9 mol,
0.20 s−1), and Ni2P/MoS2 (7.83 × 10−9 mol, 3.53 s−1). The results
reveal that Ni2P/MoS2 heterostructure formation and introduc-
tion of the porous/conductive carbon supports increase not
only the number of active sites, but also its intrinsic catalytic
activity of TOFs.
The double layer capacitance (Cdl), which is proportional to
electrochemically active surface area (ECSA), is another param-
eter that can affect the electrocatalytic performance. Cdl values are
obtained from the linear slope of the plot between scan rate and
∆j (=ja – jc) as displayed in Figure S17 (Supporting Information).
The Cdl and ECSA values for Ni2P/MoS2/N:CNT (61.7 mF cm−2
and 1542.5 cm2) and Ni2P/MoS2/N:RGO (13.8 mF cm−2 and
345 cm2) are much higher than Ni2P (0.34 mF cm−2 and
8.5 cm2), MoS2 (0.34 mF cm−2 and 8.5 cm2), Ni2P+MoS2
(0.4 mF cm−2 and 10.0 cm2), and Ni2P/MoS2 (5.9 mF cm−2
and 147.5 cm2), revealing the favorable effect of the carbon
supports. The Cdl and ECSA values of Ni2P/MoS2/N:CNT are
larger than Ni2P/MoS2/N:RGO, but the latter displays higher
HER activity than the former, indicating that all the surfaces
represented by ECSA do not become active sites of HER.[28]
Electrochemical impedance spectroscopy (EIS) was applied
to all electrocatalysts in 0.5 m H2SO4 at an overpotential of
100 mV in order to probe charge transfer characteristics, and
the Nyquist plot was fitted to an equivalent circuit model in
Figure 3e. The similar solution (series) resistance (Rs ≈ 5.1 Ω)
for each sample was determined, which was then used for iRs-
correction in polarization curves. The charge transfer resistance
Rct for Ni2P/MoS2/N:RGO (13.95 Ω) was comparable to Ni2P/
MoS2/N:CNT (14.48 Ω), but both were much lower than those
of Ni2P/MoS2 (109.3 Ω), Ni2P + MoS2 (1198 Ω), MoS2 (1202 Ω),
and Ni2P (679.2 Ω). The heterostructure Ni2P/MoS2 shows a
highly decreased Rct value. In other words, less conductive basal
plane of MoS2 changed to have an improved charge transfer
kinetics through coupling with conductive Ni2P NPs.[11d] A
little bit smaller Rct of Ni2P/MoS2/N:RGO than Ni2P/MoS2/
N:CNT may be related to better contact between both 2D MoS2
and N:RGO materials, which results in the higher electronic
conductivity.
The electrochemical stability is a great concern for any non-Pt
electrocatalysts especially in acidic solutions. Thus, stability of
the hybrid electrocatalysts was determined by an accelerated
degradation test of 3000 continuous CV cycles in the range
of 0.03 to −0.17 VRHE in 0.5 m H2SO4 in Figure 3f. The Ni2P/
MoS2/N:CNT catalyst displays a remarkable stability showing
even an improved HER performance after the 3000 CV cycles.
This could be related to the in situ electrochemical reduction
of surface oxides. The η10 value for Ni2P/MoS2/N:CNT reduces
from 93.9 to 79.3 mV after 3000 CV cycles. The 60 h long chron-
oamperometry (CA) test was conducted at a constant overpo-
tential of 150 mV as shown in Figure 3f (inset). Interestingly,
the Ni2P/MoS2/N:CNT catalyst displays the better stability with
negligible current loss (3.44%) as compared to Pt/C (14.02%)

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after continuous 60 h long CA test as displayed in Figure S18
(Supporting Information). Therefore, Ni2P/MoS2/N:RGO gives
better initial activity, but a slight degradation is observed after
3000 CV cycles, which could be attributed to the removal of
the catalyst from the surface of speedy rotating disc electrode
(RDE). The XPS analysis and HR-TEM analysis after 60 h of
continuous HER are shown in Figures S19 and S20 (Supporting
Information). In XPS analysis, the peaks for surface oxides
are evidently decreased. Moreover, HR-TEM images indicate
that there is no sign of morphological degradation during the
reaction in Ni2P/MoS2/N:CNT.
The electrochemical HER performances were also deter-
mined in 1.0 m KOH solution. Similar activity trends are
observed, but all hybrid catalysts displayed almost similar
performances with η1 (81.2–92.8 mV), η10 (149–182.7 mV),
and Tafel slopes in the range of 60.22–69.46 mV dec−1 as
displayed in Figure  4a,b and Figure S21 (Supporting Informa-
tion). The promotional effect of hybridization between Ni2P
and MoS2 is also observed in alkaline media, but the effect is
less pronounced than in the acidic electrolyte. The η10 values
of Ni2P/MoS2 hybrid catalysts (149–159 mV) are much lower
than pure Ni2P (277 mV), MoS2 (282 mV), and most of other
reported catalysts in Table S2 (Supporting Information). The
η10 and exchange current densities (J0) of all electrocatalysts
are compared in Figure 4c. The η10 values are also compared
with previously reported catalysts in 1.0 m KOH electrolyte in
Figure S22 (Supporting Information) derived from Table S2
(Supporting Information). The double layer capacitances
(Cdl) of all hybrid catalysts are in the range of 14.8–33.3 mF
cm−2 and are larger than Ni2P (0.3 mF cm−2), MoS2 (3.95 mF
cm−2), and a physical mixture of Ni2P+MoS2 (4.01 mF cm−2)
as exhibited in Figure 4d. Similarly, the charge transfer resist-
ances (Rct) of all Ni2P/MoS2 catalysts are much smaller than
individual Ni2P, MoS2, and a Ni2P+MoS2 mixture as deter-
mined by the Nyquist plots at constant voltage of −0.1 VRHE in
1.0 m KOH as in Figure S23 (Supporting Information).
3. Discussion
Physical and electrochemical characterizations discussed
above reveal structural and electronic properties of the Ni2P/
MoS2 heterostructure on N-doped carbon supports. As depicted
in Scheme 1, on the surface of a carbon support, thin MoS2
nanosheets are formed exposing their basal planes, on which
Ni2P NPs are sitting. Although distinct phases of MoS2 and
Ni2P are observed by XRD, the two phases interact strongly
through atomic mixing of all involved elements through wide
cross-doping and chemical connection between the two phases.
Thus MoS2 is doped and/or intercalated with P, N, and Ni,
whereas Ni2P is doped with S and N. The intimate interac-
tion between the two phases should result because they are
formed from the single precursor NiMoS4 containing both
metal elements, and heavy doping can make the Ni2P/MoS2

Figure 4.  HER performance of Ni2P/MoS2 heterostructures in alkaline media. a) iR-compensated polarization curves for HER and b) corresponding
Tafel slopes in 1.0 m KOH. c) Comparison of η10 values (left) and exchange currents (right) for all electrocatalysts. d) Double layer capacitance (Cdl)
calculated from the linear slope between ∆j (=ja – jc) and scan rates of all synthesized samples in 1.0 m KOH aqueous solution.

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heterostructure highly conducting. As a result, it appears that
Ni2P NPs activate HER-inert basal planes of MoS2 nanosheets
to synergistically enhance HER activity. It is also noteworthy
that the heterostructuring is more effective than the solid
solution formation, which was recently proposed as an effective
method to improve the HER activity of MoS2.[16,29] The hybridi-
zation with N-doped carbon supports increases the number of
active sites by improving dispersion of the Ni2P/MoS2 hetero-
structure, and increases its intrinsic kinetics (TOF) of HER. It
is of practical significance that the promotional effect works
more effectively in acidic electrolyte rather than alkaline media.
Although there have been several nonprecious metal electro-
catalysts that are reported to showing Pt-like HER activity and
stability in alkaline media, there is no such report in acids to
the best of our knowledge. Hence, our Ni2P/MoS2/N:CNT and
Ni2P/MoS2/N:RGO could be promising candidates for HER in
acidic media.
4. Conclusion
The electrocatalytic activity of 2D MoS2 is enhanced by activating
its HER-inert basal planes through heterostructuring with Ni2P
nanoparticles. Thus, a single precursor NiMoS4 provides a
platform to construct Ni2P/MoS2 heterostructure via phosphi-
dation reaction with in situ produced PH3. The conductivity
and stability of the material are further enhanced by hybridi-
zation with N-doped graphene or CNTs. These heteroatoms
(N, S, P, and O) also help to promote the HER performance by
providing the ample proton (H+) adsorption sites through their
lone-pair electrons especially in acidic media. As a result, Ni2P/
MoS2/N:RGO and Ni2P/MoS2/N:CNT demonstrate outstanding
HER activity and stability in acid electrolytes, comparable with
incumbent Pt/C and even better in high current density region
(>200 mA cm−2). The result makes them a promising candidate
for practical hydrogen production via water electrolysis in acidic
media.
5. Experimental Section
Synthesis of Ni2P/MoS2 Heterostructures as Nanoparticles and
on a Carbon Substrate: To obtain NiMoS4 as a single precursor
to Ni2P/MoS2, (NH4)2MoS4 (0.768 mmol, Sigma-Aldrich) and
Ni(CH3CO2)2·4H2O (0.768 mmol, Sigma-Aldrich) were dissolved in
50 mL of ethanol and distilled water (1:1 volumetric ratio) in a glass
beaker with continuous stirring at 80 °C to evaporate the solvent.
A mixture of the obtained NiMoS4 powder and NaH2PO2·H2O
(1.537 mmol, Sigma-Aldrich) in an alumina boat was heated in a tube
furnace to a desired temperature (450–550 °C) for 2 h with a ramping
rate of 2 °C min−1 in H2 environment. To remove the unreacted
chemicals, the as-obtained Ni2P/MoS2 powder was sonicated in 0.1 m
H2SO4 solution for 30 min and washed several times with distilled
water. Then the heterostructure catalyst was dried at 60 °C in an
oven and denoted as Ni2P/MoS2-X, where X represents a reaction
temperature, 450, 500, or 550 °C.
To prepare Ni2P/MoS2 on a carbon substrate, graphene oxide (GO)
was prepared from natural graphite flakes using a modified Hummer’s
method[30] and CNTs were oxidized by using 1:1 volumetric ratio of
distilled water and HNO3 (69%, Matsunoen Chemicals).[31] N:RGO
and N:CNT were synthesized by simply annealing the GO or oxidized
CNT in NH3 gas at 800 °C for 4 h.[32] The synthetic procedures for both
Adv. Funct. Mater. 2019, 1809151 1809151  (7 of 8)
www.afm-journal.de
Ni2P/MoS2/N:RGO and Ni2P/MoS2/N:CNT were the same as for Ni2P/
MoS2 except addition of a required amount of exfoliated N:RGO or
N:CNT in the NiMoS4 formation step.
Single Phase Ni2P and MoS2: For Ni2P, 300 mg of NiCl2 (2.315 mmol,
Sigma-Aldrich) and 490.7 mg of NaH2PO2·H2O (4.629 mmol, Sigma-
Aldrich) were mixed and annealed at 300 °C for 2 h with a ramping rate
of 2 °C min−1 in the tube furnace. Then, it was sonicated in 0.1 m H2SO4
aqueous solution for 30 min, followed by washing with distilled water
and vacuum drying at 60 °C for 12 h. MoS2 was obtained by thermal
decomposition of (NH4)2MoS4 (1.152 mmol, Sigma-Aldrich) at 500 °C
under H2 flow for 2 h with a ramping rate of 2 °C min−1 in the tube
furnace.
Physical Characterization: Crystallographic information of as
synthesized hybrid electrocatalysts was determined by powder XRD
(PANalytical pw 3040/60 X’pert) using Cu Kα radiation. The Raman
spectra (AFM-Raman, WITec, alpha300S) were obtained by using
532 nm laser. TGA (Q500) was performed in air and N2 at a ramping
rate of 10°C min−1 up to 900 °C. Chemical surface composition and
oxidation states were determined by XPS (Thermo-Fisher, K-alpha).
A field-emission scanning electron microscope (Hitachi, S-4800, 15 kV)
was used to observe the surface morphology. A TEM (JEOL, JEM-2100)
and HR-TEM (JEOL, JEM-2100F) were utilized to investigate structural
information, chemical compositions, and elemental mapping of
samples.
Electrochemical Measurements: The electrochemical analysis was
performed in a three-electrode cell using an RDE (PAR Model 636 RDE)
linked with a potentiostat (Ivium Technologies) at room temperature.
An Ag/AgCl (3.0 m NaCl) electrode and a graphite rod were used
as reference and counter electrodes, respectively. The catalyst’s ink
was prepared as follows: 10 mg of as-synthesized electrocatalysts was
sonicated for 1 h in 2:1:1 v/v mixture (1.0 mL) of distilled water, ethanol,
and isopropyl alcohol containing 10 µL of 5% Nafion solution. The
obtained ink (10 µL) was drop-casted onto a glassy carbon electrode
(0.5 mm diameter) and dried at 60 °C for 10 min to make the working
electrode with a catalyst loading of about 526.3 µg cm−2. All potentials
were referenced to a reversible hydrogen electrode (RHE) by the
equation ERHE = E(Ag/AgCl) + 0.059 pH + 0.209.
The polarization curves for HER were measured in aqueous 0.5 m
H2SO4 (pH = 0) and 1.0 m KOH (pH = 14) at a scan rate of 5 mV s−1
with a rotation speed of 1600 rpm. The electrochemical stability tests
were conducted up to 3000 CV cycles in the range of 0.03 to −0.17 VRHE.
The chronoamperometry test was conducted at −0.15 VRHE for 60 h.
EIS was carried out in the frequency range of 100 kHz to 1 mHz with
a modulation amplitude of 10 mV. Z-view software was used to fit the
EIS spectra. To evaluate the ECSA, CV cycles were performed from
0.0 to 0.2 V (in 0.5 m H2SO4) and −0.8 to −0.6 V (in 1.0 m KOH) versus
Ag/AgCl with different sweep rates between 20 and 100 mV s−1.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
M.K.K. and M.A.R.A. contributed equally to this work. J.S.L. conceived
the project and oversaw all the research phases. M.K.K. and M.A.R.A.
conceived the idea for the study, designed the experiments, and
analyzed the data. M.K.K. synthesized all materials and performed
the electrochemical measurements and the XRD, XPS, SEM, and TEM
analyses. M.H.L. assisted with HR-TEM imaging. J.S.L., M.K.K., and
M.A.R.A. wrote the manuscript and discussed the results. All the authors
contributed and commented on the manuscript. This research was
supported by a Basic Science Grant (NRF-2018R1A2A1A05077909), the
Climate Change Response Project (2015M1A2A2074663), Korea Center
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
for Artificial Photosynthesis (KCAP, No. 2009-0093880), and Korea-China
Key Joint Research Program (2017K2A9A2A11070341), which are funded
by the Ministry of Science and ICT, Republic of Korea; and Project No.
10050509 and KIAT N0001754 of the Ministry of Trade, Industry and
Energy, Republic of Korea.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
electrocatalysts, heterostructure, hydrogen evolution reaction,
molybdenum sulfide, nickel phosphide
Received: December 23, 2018
Published online:
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