Research Article

pubs.acs.org/acscatalysis

Sulfur and Nitrogen Dual-Doped Molybdenum Phosphide

Nanocrystallites as an Active and Stable Hydrogen Evolution
Reaction Electrocatalyst in Acidic and Alkaline Media
Mohsin Ali Raza Anjum and Jae Sung Lee*
School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), 50 UNIST-gil, Ulsan
44919, South Korea
*
S Supporting Information
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ABSTRACT: Sulfur and nitrogen dual-doped molybdenum

phosphides (MoP/SN) are synthesized via a (thio)urea-
phosphate-assisted strategy in which the reductant (thio)urea
acts as S and N source and phosphoric acid provides the P
atom. The MoP/SN nanoparticles are generated by in situ
phosphidation of indigenously synthesized ammonium phos-
phate-coated P-doped MoSx nanoparticles in a hydrogen
atmosphere. Then, MoP/SN is anchored on graphene to
obtain a hybrid electrocatalyst (MoP/SNG) that exhibits high
activity and stability for electrochemical hydrogen evolution
from water in both acidic and basic electrolytes, outperforming most MoP-based electrocatalysts reported in the literature. The
dual doping and hybridization with graphene enhance electron conductivity of MoP and stabilize small MoP nanoparticles to
increase activity and stability, especially in acid electrolytes.
KEYWORDS: molybdenum phosphide, S and N dual doping, hydrogen evolution reaction, electrocatalysts, urea-phosphate route

T he electrochemical hydrogen evolution reaction (HER)

from water splitting has attracted significant attention
recently for producing sustainable hydrogen with electricity
generated from renewable energy sources. The biggest
challenge in HER research is to replace the most common
and best incumbent Pt catalysts with inexpensive nonprecious
metals.1 Transition metal carbides, sulfides, borides, nitrides,
and phosphides have been extensively studied as candidates for
non-Pt electrocatalysts.1−5 Transition metal phosphides
(TMPs) have attracted significant attention over the past few
years due to their superior electrical conductivity, mechanical
strength, and chemical stability relative to those of other
transition metal compounds.4−6 They are proven to be high-
performance electrocatalysts with excellent activity, stability,
and nearly 100% Faradaic efficiency in acidic, alkaline, and
neutral media for HER.6−11 Experimental and theoretical
investigations have revealed that the atomic percentage of P
atoms in the lattice of transition metals (Fe, Co, Ni, Cu, Mo,
and W) plays a crucial role with the more electronegative P
atom acting as a basic trap of positively charged protons during
the reaction.6,12−14 Furthermore, an appropriate atomic ratio of
metals and P, especially in metal-rich phosphides, offers
excellent conductivity and more noble metal-like properties
relative to those of the parent transition metals.15 Despite the
success of TMPs as good electrocatalysts for HER, there are
still many remaining challenges to improve their performance
and stability further by tuning their electronic structures,
maximizing electrical conductivity, doping with other elements,
and protecting P3− in TMP, the least stable oxidation state of P,
from oxidation.
Introduction of more electronegative P atoms into metals
may greatly restrict the electron delocalization in the metal,
resulting in lower conductivity.16 However, with an appropriate
atomic ratio of metal and P or doping of other heteroatoms
such as S or N, TMPs can exhibit a metallic character or even
superconductivity, especially for the metal-rich phosphides.17
Recently, similar strategies have been applied to enhance the
HER activity of MoP: (i) doping with S to form molybdenum
phosphosulfide (MoP|S) on the surface of MoP by a
postsulfidation8 or postphosphidation of MoS2 to form
MoS2(1−x)Px solid solution,18 (ii) compounding with carbon
materials like graphene19 or porous carbons,20 and (iii)
promotion with a TM (Co, Fe, or W).21−24 The TMP
nanostructures are generally synthesized via three common
ways: (i) Solution-phase synthesis using organic phosphine like
tri-n-octylphosphine (TOP), triphenylphosphine (TPP) or tri-
n-octylphosphine oxide (TOPO) as a P source in high-boiling-
point solvents (e.g., oleylamine) in an inert atmosphere.17,25
(ii) Gas−solid reaction, in which extremely toxic and lethal PH3
gas is used as P source directly or produced in situ from
hypophosphite;26 in this method, post-treatment is mandatory
with inert gas to remove residual PH3. (iii) High-temperature
reduction of metal phosphates to form bulk TMP.17
Received: February 19, 2017
Published: March 16, 2017

© 2017 American Chemical Society 3030 DOI: 10.1021/acscatal.7b00555

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Herein, a simple, economical, and eco-friendly (thio)urea-
phosphate-assisted strategy is demonstrated to synthesize S and
N codoped MoP (MoP/SN) nanocrystallites, which display
excellent electrocatalytic activity and stability for HER in both
acidic and alkaline media. The MoP nanocrystallites show their
best performance when they are grown on S and N dual-doped
graphene (MoP/SNG), displaying one of the best HER
activities among reported non-noble metal electrocatalysts
and still maintaining excellent stability in aqueous acidic and
alkaline solutions. In particular, the stability in acids makes
them a promising practical electrocatalyst because there are
only a few acid-stable nonprecious metal electrocatalysts known
to date.
Distinct from earlier studies, our synthesis relies on an in situ
sulfidation reaction between polyoxometalates (POMs) and
(thio)urea-phosphates to form ammonium phosphate-coated,
reduced P-doped MoSx, followed by the reductive phosphida-
tion in a H2 atmosphere. To the best of our knowledge, this is
the first systematic report on the fabrication of MoP
electrocatalysts by using phosphoric acid as a P source and
reductant (thio)urea as S and N sources while controlling the
phase and size of the nanoparticles. In addition, this method
induces self-doping of N and S atoms into the skeleton of
phosphides as well as a graphene support that plays crucial roles
in stabilizing the MoP nanoparticles (NPs) and P3− state by
making Mo/P−N and Mo/P−S bonds to increase the electrical
conductivity and provide ample S and N sites for proton
adsorption. Avoiding the use of expensive, toxic, and corrosive
chemicals like PH3, hypophosphites, organic phosphine, and
high-boiling organic solvents is another advantage of this
synthesis method of MoP nanoparticles. The present synthetic
strategy could also be applied to other transition metal (e.g.,
Co, Fe, Ni, and W) phosphides for large scale production due
to its simplicity and the use of cheap and environmentally
benign precursors.
■
RESULTS AND DISCUSSION
Urea-Phosphate-Assisted Synthesis for Molybdenum
Phosphide. Polyoxometalates (POMs) are early transition
metal (Mo, W) polyatomic anionic clusters composed of one
metal oxide and a main group oxyanion (phosphate or silicates)
and are good oxidants and versatile inorganic building blocks
for the construction of various hybrid materials.27−29 Thiourea
is a reducing agent that liberates H2S gas and urea, especially in
the presence of acids (H3PO4 and POM).29 These properties
led us to design a procedure to synthesize S and N codoped
MoP nanocrystallites (MoP/SN) by simply using phosphomo-
lybdic acid (H3PMo12O40·nH2O) to produce ammonium
phosphate-coated, P-doped MoSx (precursor) via hydrothermal
reduction with thiourea followed by hydrogen reduction of the
precursor as illustrated in Scheme 1 and described in detail in
the Experimental Section. A Keggin-type H3PMo12O40 is
reduced with thiourea (eq 1) to form a bluish mixed-valence
reduced species [PMo12O40]6− without the loss of the Keggin
structure.30 During continuous boiling under autogenous
pressure, [PMo12O40]6− turns to P-doped MoSx nanoparticles
(NPs) by reduction with H2S gas liberated from thiourea in the
acidic solution (eq 2) with urea-phosphate as a side product.
Ammonium o-polyphosphates and biuret encapsulate the P-
doped MoSx NPs upon pyrolysis of urea-phosphate (eq 3).31
Then, ammonium phosphate-encaged P-doped MoSx NPs are
converted to MoP/SN upon reduction by H2. An exfoliated
graphene oxide (GO) suspension is introduced directly into the
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Scheme 1. Schematic Illustration of (Thio)urea-Phosphate-
Assisted Synthesis of MoP/SN and MoP/SNG
hydrothermal step to obtain MoP/SN NPs supported on
graphene (MoP/SNG).
H+
[PMo12O40]3 − + (NH 2)2 CS ⎯→
⎯ [PMo12O40]6 − + H 2S + (NH 2)2 CO
(1)
Δ
[PMo12O40]6 − + x H 2S → P − MoSx + y H 2O (2)
Δ
(NH 2)2 CO + H3PO4 → (NH 2)2 ·HPO4 (amm. phosphate) + gases
(3)
These phase changes during the synthesis steps were
confirmed by powder X-ray diffraction (XRD) patterns of
MoP/SN electrocatalysts at different reduction temperatures
under H2 as shown in Figure 1a. Pure MoP of a hexagonal WC-
type structure (space group P6̅m2) is obtained above 600 °C,
and small peaks of molybdenum phosphate are observed in the
samples reduced below 600 °C. Doping of N and S does not
significantly alter the bulk crystal structure of MoP. The
crystallite size of MoP was obtained by applying the Scherrer
equation to X-ray line broadening, which increases along with
the reduction temperature as shown in Figure 1b. The XRD
pattern of P-doped MoSx shows P−Mo3S4 as the main phase
(Figure S1a), and MoP/N-650 and graphene-supported
catalysts show the same phase behavior as the unsupported
MoP/SN catalysts as shown in Figure S1b and c.
Scanning electron microscopy (SEM) images of the as-
synthesized MoP/SN-650 °C and MoP/SNG-20 (with 20 wt %
graphene) catalysts show that particles form a closely
interconnected porous network (Figure S2). No difference in
morphology is observed after loading the SN-doped MoP
nanoparticles on graphene (MoP-SN/G-20, Figure S4a and b).
The surface morphologies of MoP/N-650 (N-doping only) and
a physical mixture of MoP-SN/G-20 are also shown in Figures
S3 and S4a and b. Elemental mappings by energy-dispersive X-
ray spectroscopy (EDX)-SEM images of MoP/SN-650 (Figure
S5) and MoP/SNG-20 (Figure S6) clearly indicate uniform
elemental distributions throughout the particles. (EDS)-STEM
mappings of MoP/SNG-20 and MoP/SN-650 in Figures S7a
and S8 also demonstrate similar uniform elemental distribu-
tions. Thus, MoP NPs are homogeneously distributed over
graphene and uniformly doped with S, N, and C. EDS-STEM
of MoP/SNG-20 (Figure S7b) clearly indicates that there is no
significant change in the elemental composition after the HER
durability test.
The nature of chemical bonding in as-prepared MoP/SN and
MoP/SNG-20 was investigated by X-ray photoelectron spec-
troscopy (XPS) in Figure 2. The Mo 3d region (Figure 2a) for
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Figure 1. XRD patterns of MoP synthesized at different reduction temperatures (a) and their particle sizes calculated by applying the Scherrer
equation to each diffraction peak (b).
Figure 2. High-resolution XPS of MoP/SN-650 and MoP/SNG-20: (a) Mo 3d, (b) P 2p, (c) N 1s, (d) S 2p for MoP/SNG-20, and (e) XPS survey
spectra.
both MoP/SN and MoP/SNG indicates a prominent doublet
at 228.2 and 231.3 eV of Moδ+ (0<δ ≤ 4), which can be
assigned to Mo of MoP.6,8,18 A doublet of Mo4+3d5/2 and
Mo4+3d3/2 with peaks18 at 229.2 and 232.4 eV reveals the
successful insertion of the S atom into the structure of MoP,
and almost all molybdenum sulfide is converted to MoP during
the in situ reductive phosphidation reaction. A weak signal of
surface oxides can also be observed at 235.8/232.5 eV,6 which
can be assigned to the high oxidation state of Mo (MoO3).
These surface oxides, invisible in XRD patterns (Figure 1a), can
be removed by chemical and electrochemical treatment.32,33 An
XPS depth profiling of the samples was further performed in
Figure S9, which reveals that the oxygen is present only at the
surface of the catalysts. The content of oxygen is greatly
reduced with etching time as depicted in Figure S9a and d.
The doublet at 129.4 and 130.2 eV in the P 2p (Figure 2b)
and one doublet (161.8 and 163.0 eV) in the S 2p (Figure 2d
and Figure S10a) spectra indicate a similar oxidation state and
elemental environment of P and S atoms in MoP/SN and
MoP/SNG-20.8,18 The former confirms the predominant P3+
species bonded to Mo, and the latter arises from a sulfide
species (S2−) in both samples.8 Four additional peaks of P−S,
P−C, P−O, and P−N/PON at 131.30, 132.8, 133.8, and 134.6
eV, respectively, are observed in the P 2p spectra, indicating
that a P species is likely to be stabilized by sharing electrons
with more electronegative S, C, O, and N atoms.8,20,34−36
Similarly, in the S 2p spectrum of MoP/SNG-20 (Figure 2d), a
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combined peak of -C−S/-C−SO at 164 eV and a peak of -C−
SO2 at 168.6 eV confirm the successful doping of S2− species
into the graphene structure.37,38 Thus, graphene itself is doped
with S and N, probably associated with dopant atoms around
defects such as −C−S-C- and -CS- structures.38 In XPS C 1s
spectra (Figure S10b and c), the main peak of graphitic sp2
carbon is centered at 284.6 eV, whereas an additional
component at 285.6 eV is assigned to C−N and/or CN.
The absence of signal at 287.9 eV, typically O−CO, suggests
that all oxygenated groups on GO have been removed during
the reduction reactions. The XPS N 1s spectrum (Figure 2c)
could be fitted to Mo−N (394.0 eV), MoS2 (395.3 eV),
pyridinic (398.3), pyrrolic (399.5 eV), graphitic (401.2 eV),
and a broad peak of -SCN (397.8 eV).39−41 From the above
XPS study, it is confirmed that more electronegative dopants
(S, N, and C) stabilize the P3− state through P−S, P−N/PON,
and P−C bonds by withdrawing electron density from P and
donating back to vacant d orbitals of Mo, which provides
superior conductivity and enhanced stability as shown later.
The morphology of MoP particles was further probed by
high-resolution transmission electron microscopy (HR-TEM).
Panels a and b in Figure 3 clearly show rod-shaped
nanocrystallites in the samples MoP/SN-650, MoP/SNG-5,
and a physical mixture of MoP-SN/G-20 (Figure S4c and d)
embedded in the carbon matrix. These nanorods are converted
to nanoparticles (3−7 nm) when an increased amount of GO is
added during the synthesis reaction as depicted in Figure 3c
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Figure 3. TEM images of (a) MoP/SN-650, (b) MoP/SNG-5, (c) MoP/SNG-20 (inset: particle size distribution), (d) MoP/SNG-30, (e, f) HR-
TEM images of MoP with (100) and (101) planes and corresponding fast Fourier transformation (FFT) patterns, and (g, h) structures of MoP and
MoP/SN.
and d. The lattice spacings of 0.27 and 0.21 nm and
corresponding fast Fourier transforms (FFT) are assigned to
(100) and (101) planes for hexagonal MoP in Figure 3e and f.
No specific change was observed in lattice parameters of MoP
after insertion of S and N atoms in the crystal structure as
confirmed by the XRD pattern (Figure 1 and Figure S1b and
c).
Electrochemical Hydrogen Evolution Reaction from
Water in Acidic and Alkaline Media. The HER activities of
MoP/SN electrocatalysts prepared at different reduction
temperatures were evaluated in 0.5 M H2SO4 and 1.0 M
KOH aqueous solutions using a three-electrode electrochemical
cell (iR-corrected, Figure 4a). As expected, MoP/SN-550 shows
little HER activity, whereas performance is greatly enhanced
with complete reduction of phosphates into MoP (Figure 1a) at
higher temperatures. In particular, MoP/SN-650 shows the
highest activity in 0.5 M H2SO4 with the lowest onset potential
of ∼44 mV and overpotentials of 57 and 104 mV to produce
current densities of 1 and 10 mA/cm2 (η1 and η10), respectively.
Interestingly, the HER activity in alkaline solution (Figure 4a)
reaches its maximum at reduction temperatures of 575−650
°C. The optimal reduction temperature of 650 °C is low
enough to allow the formation of the tiny NPs (Figure 1b)
while being high enough to remove all minor surface oxides and
phosphates on the MoP NP surface.32,33 The overpotentials of
η1 ≈ 17−20 mV and η10 ≈ 90−94 mV are needed to deliver
current densities of 1 and 10 mA/cm2 for MoP/SN-575 to
MoP/SN-650. However, further increasing the reduction
temperature results in decreased HER activity due to sintering
of MoP and removal of S and N species as exhaust gases.38 The
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codoped MoP/SN-650 sample contains ∼7.9 wt % N and ∼8.5
wt % S dopants confirmed by XPS depth profiling in Figure S9f.
The coupling of N with the S dopants into the structure of
MoP plays a critical role in the high HER activity by
coordinating with least stable P3−, enhancing electrical
conductivity and generating more adsorption sites for protons.
For comparison, N-doped MoP (MoP/N-650) nanoparticles
are also prepared by using urea-phosphate instead of thiourea-
phosphate by adopting the same procedure. In Figure S11a, η10
and η20 are 164 and 185 mV in acidic media and 154 and 182
mV in alkaline media, respectively, highlighting the synergistic
effect of S and N codoping. The higher HER performances of S
and N codoped MoP NPs in acidic media than those of single
N-doped MoP/N-650 and earlier reported MoS2(1−x)Px solid
solution (η10 ≈ 150 mV)18 clearly indicates the dominant effect
of dual doping.
The performance of MoP electrocatalysts can be further
enhanced by combining them with a conductive graphene
substrate. Thus, MoP-SN nanoparticles are directly grown on
graphene by adding graphene oxide (GO) in the hydrothermal
reactor. During the synthesis process, graphene is also codoped
with S and N as indicated by XPS analysis in Figure 2. The
catalysts are denoted as MoP/SNG-x (x = 5, 10, 20, and 30),
where x denotes the wt % of graphene. The performance curves
in Figure 4b clearly show remarkable improvement in HER
activity when MoP NPs are grown on S and N codoped
graphene giving η10 and η100 of 99 and 157 mV, respectively, for
the MoP/SNG-20 catalyst in 0.5 M H2SO4. It is noted that this
activity is substantially higher than those of previously reported
MoP-based catalysts in terms of all activity parameters as
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Figure 4. HER iR-corrected polarization curves of (a) MoP/SN synthesized at different reduction temperatures and (b) MoP/SNG-x (x = 5, 10, 20,
and 30 wt %) in acid and base electrolytes. Overpotentials required for current densities of 10, 50, and 100 mA/cm2 in (c) 0.5 M H2SO4 and (d) 1.0
M KOH. (e) Tafel slopes in acid and base and (f) measured capacitive currents (ΔJ/2) plotted as a function of scan rate.
summarized in Tables S1 and S2. In 1.0 M KOH, MoP/SNG-x
hybrids exhibit excellent HER performances with the lowest
onset potential close to that of commercial Pt/C and by
reducing η10 to only 63, 52, 49, and 52 mV for catalysts having
SNG of 5, 10, 20, and 30 wt % with similar mass loadings on
the disc electrode. A comparison of overpotentials at current
densities of 10, 50, and 100 mA/cm2 is presented in Figure 4c
and d in acid and alkaline media, and MoP/SNG-20 shows the
best performance approaching that of Pt/C (Figure 4b). The
MoP-SN and graphene hybrid electrocatalyst was also prepared
by reduction of the physical mixture of ammonium phosphate-
coated P-doped MoSx (a precursor of MoP/SN) with exfoliated
GO, denoted as MoP-SN/G. As depicted in Figure S11b, the
physical mixture with 20 wt % graphene (MoP-SN/G-20) does
not show any significant enhancement of HER activity in acidic
media at low current densities, but the effect of graphene is
more pronounced in alkaline solution leading to reduction of
η10 by 20 mV for MoP-SN/G-20. However, it is clear that the
direct growth of MoP-SN NPs on graphene yields higher
performing electrocatalysts than a physical mixture of
presynthesized MoP/SN precursor and graphene.
For understanding the HER mechanism in 0.5 M H2SO4 and
1.0 M KOH, Tafel analysis was conducted in Figure 4e, The
Tafel slopes of MoP/SN-650 (45 mV/dec), MoP/SNG-5 (51
mV/dec), MoP/SNG-10 (58 mV/dec), MoP/SNG-20 (54
mV/dec), and MoP/SNG-30 (54 mV/dec) suggest that HER
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reactions follow the Volmer−Heyrovsky mechanism in acidic
media. In 1.0 M KOH, all samples except MoP/SNG-20 exhibit
Tafel slopes in the range of 39−59 mV/dec, suggesting a
similar mechanism as in acids. The MoP/SNG-20 displays the
highest activity with the most positive onset potential and
lowest Tafel slope equal to the commercial Pt/C catalyst, i.e.,
∼31 mV/dec The bare MoP/SN-650 without SNG has a
slightly lower activity and a higher Tafel slope than MoP/SNG,
which reveals that the hybrid structure formed between MoP
and SNG reduces the energy required to activate HER by
increasing the conductivity, stabilizing NPs through Mo-P-X-
Mo (X = S, N, and C) bonding (Figure 3g,h) and providing
more proton (H+) adsorption sites. Evidence of such a
synergistic coupling effect is already discussed with the
electrochemical and spectroscopic data. All electrocatalysts
display the high exchange current densities (J0), which are
expected to be proportional to the catalytic active surface area
and represent high kinetics of charge transfer reactions over all
electrodes. The higher J0 of MoP/SNG-20 (0.15 and 0.46 mA/
cm2) than that of pristine MoP/SN-650 (0.056 and 0.48 mA/
cm2) in acid and base, respectively, confirm that the HER
kinetics become faster due to electronic and chemical
promotional effects. The summarized electrochemical data in
acidic and alkaline media of as-synthesized catalysts are
tabulated in Tables S3 and S4.
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Figure 5. Electrochemical impedance spectroscopy (EIS) of catalysts at overpotentials of 120 and 125 mV in (a) 0.5 M H2SO4 and (b) 1.0 M KOH.
(c) Equivalent circuit (inset) used for fitting of EIS data. Rs is the overall series resistance; CPEd and Rd are the constant phase element and diffusion
resistance, respectively. CPEdl is the constant phase element, and Rct is the charge transfer resistance of the MoP/electrolyte interface.

Figure 6. Cathodic linear sweeping voltammograms of (a) MoP/SN-650 and (b) MoP/SNG-20 after 2000 CV cycles in 0.5 M H2SO4 and 1.0 M
KOH solutions. (c) Stability comparison after 1000 CV scans for HER and (d) after a 20 h durability test (by chronoamperometry as inset) for
MoP/SNG-20 in acidic and alkaline media.

Electrochemically active surface area (ECSA) is a useful
parameter for representing the intrinsic activity of the catalysts
determined by measuring the double layer capacitance (Cdl) at
the electrolyte−electrode interface with cyclic voltammetry
(CV). The detailed calculation procedure of ECSA is described
in the Supporting Information. As shown in Figure 4f and
Table S3, Cdl and ECSA values increase with higher loading of
SNG. The Cdl and ECSA of MoP/SN-650 (3.96 mF/cm2, 99
cm2), MoP/SNG-5 (4.53 mF/cm2, 113.25 cm2), MoP/SNG-10
(8.89 mF/cm2, 222.25 cm2), MoP/SNG-20 (20.5 mF/cm2,
512.5 cm2), and MoP/SNG-30 (18.58 mF/cm2, 464.5 cm2)
also confirm that the activity and exchange current density of
the electrocatalysts are directly related to ECSA (Table S3).
The cyclic voltammetry (CV) values of MoP/SN-650, MoP/
SNG-10, and MoP/SNG-20 in acidic and alkaline media are
compared in Figure S12. The broad redox features between
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−0.05 and 0.15 VRHE similar to Pt/C and MoP8 were observed
in the HER hysteresis for the cathodic- and anodic-going scans,
especially for graphene hybrid electrocatalysts. The anodic
sweep of the MoP/SN-650 catalyst exhibits higher activity than
the cathodic sweep in both acidic and alkaline media, which
may come from possible reduction of surface PO43− species
observed by XPS generating more active states during the
cathodic-going sweep.
Electrochemical impedance spectroscopy (EIS) was applied
for all electrocatalysts in acidic and basic media at different
overpotentials (Figure S13). The Nyquist plots of MoP/SN-
650 and MoP/SNG-x (x = 5, 10, 20, and 30) at a given
overpotential (η) of 120 mVRHE in 0.5 M H2SO4 and at 125
mVRHE in 1.0 M KOH solutions are compared in Figure 5a and
b. The EIS Nyquist plots and their equivalent circuit model
(Figure 5c, inset) show that there are two time constants. The
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first one at high frequencies is related to the surface porosity
(Rd) of the materials and the second one at low frequencies
corresponds to the charge transfer (Rct) process at the cathode.
The relatively lower Rct and Rd values of MoP/SNG-x than bare
MoP/SN-650 in all electrolytes could be mainly related to the
high conductivity of S and N codoped graphene and larger
ECSA with better dispersion of smaller nanoparticles. The
diffusion resistance (Warburg impedance) for MoP/SN-650 is
larger than that for MoP/SNG hybrids in both electrolytes
because of its larger particle sizes.42 Ion diffusion in electrolyte
also becomes slower for small ECSA and large particles.42 The
results of EIS studies are consistent with the performances of
the electrocatalysts, indicating that charge transfer is the critical
factor determining the HER activity.
For the electrochemical durability of MoP-based electro-
catalysts to be tested, accelerated cyclic voltammetry (CV) was
performed continuously for 2000 cycles at a scan rate of 100
mV/s in acidic as well as alkaline media as displayed in Figure 6.
The MoP/SN-650 electrocatalyst exhibits excellent stability in
acidic electrolyte with a minor negative shift in overpotential
after the 50th cycle. On the other hand, it displays a small but
continuous loss of activity in alkaline media, indicating
continuous corrosion of this catalyst. Similarly, the time
dependence of current density (chronoamperometry, CA) for
MoP/SNG-20 was also conducted for 20 h as a long-term
durability test at a static overpotential in both media (inset of
Figure 6d). As mentioned, the morphology and atomic
distribution in the electrocatalyst also remains unchanged
during the period as shown in EDS-STEM of MoP/SNG-20
(Figure S7b). The performance and stability dramatically
increase in both acidic and alkaline electrolytes when these
NPs are anchored on S and N codoped graphene (MoP/SNG-x
series) as shown in Figure 6b. CV curves (Figure S14) in the
range −0.15 and 0.15 V represent the irreversible reduction of
surface phosphate (PO43−) species to P3−, and the current
difference between anodic and cathodic currents ΔJ (Ja − Jc)
becomes stabilized after the first 500 CV cycles. The stability of
MoP/SN-650 with and without graphene was compared in
both electrolytes in Figure 6c. It shows that MoP-SN
nanoparticles directly grown on the carbon substrate (MoP/
SNG) are more stable than the physical mixture MoP-SN/G or
bare MoP/SN-650, indicating a close contact between MoP
and S and N doped graphene is important to take full advantage
of the promotional effect of graphene. Because there are only a
few nonprecious metal electrocatalysts stable in acids, our
MoP/SNG could be a promising candidate for HER in acidic
electrolytes.
■
CONCLUSIONS
S and N codoped MoP has been synthesized, adopting a unique
(thio)urea-phosphate-assisted process in which thiourea acts as
a reducing agent for phosphomolybdic acid as well as an S and
N source and phosphoric acid (H3PO4) as a P source. This
method relies on the reduction of in situ-produced ammonium
phosphate-coated P-doped MoSx nanoparticles to provide
uniform doping of S and N at an atomic level into the MoP
structure. It is also confirmed by XPS data that more
electronegative dopants (S, N, and C) stabilize P3− through
P−S, P−N/PON, and P−C bonds by withdrawing electron
density on P and donating back to vacant d orbitals of Mo. The
HER performance and stability of the MoP/SN NPs is further
improved by loading them onto conductive graphene to reduce
the particle size of MoP, increase the electrochemical active
3036
Research Article
surface area, and improve electron/proton conductivity. As a
result, S and N doped MoP directly grown on graphene (MoP/
SNG-20) demonstrates excellent activity and stability in
electrochemical HER from water in both acidic and alkaline
electrolytes outperforming most MoP-based electrocatalysts
reported to date.
■ EXPERIMENTAL SECTION
Synthesis of S and N Codoped MoP NPs and Their
Graphene Composite. All chemicals were utilized as
purchased without further purification. Thiourea-phosphate
was synthesized by mixing thiourea with phosphoric acid.
Typically, 85% phosphoric acid (5.5 mmol, 634.12 mg, Sigma-
Aldrich) was dissolved in triply distilled water (20 mL) in a
glass beaker (250 mL) equipped with a magnetic stirring bar,
and an aqueous solution thiourea (5.0 mmol, 380.60 mg,
Sigma) was then added. The reaction mixture was heated to 60
°C until a clear solution was obtained and was maintained at
this temperature for 1 h. A transparent yellow solution of
phosphomolybdic acid (PMo12, 0.5 mmol, 913 mg, Sigma-
Aldrich) in water was added slowly. The reaction mixture
became bluish green at once, an indication of the reduction of
PMo12 from [PMo12O40]3− to [PMo12O40]6−. For the synthesis
of ammonium phosphate-coated P-doped MoSx NPs, the as-
prepared solution was hydrothermally treated at 180 °C for 15
h. The reduced PMo12 was converted to P-doped MoSx (see
XRD in Figure S1a) by internally produced H2S gas, and the
remaining phosphoric acid reacted with indigenously generated
ammonia (NH3) gas to form ammonium phosphate. Then, this
freshly prepared suspension of pH 7 was dried at 60 °C to be
used for MoP synthesis.
The as-prepared ammonium phosphate-coated P-doped
MoSx was reduced in a tube furnace under H2 gas with a
ramping rate of 5 °C/min, kept at a required temperature
(550−700 °C) for 3 h, and then naturally cooled to obtain
diamond blackish powders, denoted as MoP/SN-X (X denotes
reduction temperature). For comparison, N-doped MoP
nanoparticles are also prepared by using urea instead of
thiourea following the same procedure.
MoP NPs were grown on S and N codoped graphene (MoP/
SNG) by adding the required amount of exfoliated graphene
oxide (GO) suspension directly into the hydrothermal step and
then reduced following the same conditions. For MoP-SN/G,
the ammonium phosphate-coated P-MoSx powder physically
mixed with exfoliated GO suspension (20 wt % G of MoP/SN-
650) was then dried at 60 °C before reduction in a H2
atmosphere.
Characterization. Crystallographic information of the as-
synthesized electrocatalysts was investigated by powder X-ray
diffraction (XRD, PANalytical pw 3040/60 X’pert) with Cu Kα
radiation. The surface morphologies and structural information
were recorded with a field-emission scanning electron micro-
scope (FE-SEM, Hitachi, S-4800, 15 kV) and a transmission
electron microscope (TEM, JEOL, JEM-2100). The chemical
compositions, elemental mapping, and in-depth crystal
information on samples were collected by high-resolution
transmission electron microscopy (HRTEM, JEOL, JEM-
2100F). X-ray photoelectron spectroscopy (XPS, Thermo-
Fisher, Kα) was used to identify the surface atomic composition
and chemical states.
Electrochemical Measurements. The catalyst ink was
prepared by dispersing electrocatalysts (1.0 mg/mL) in a
mixture of 7:3 deionized water/2-propanol and 10 μL of 5%
DOI: 10.1021/acscatal.7b00555
ACS Catal. 2017, 7, 3030−3038
ACS Catalysis
Nafion solution. The mixture was sonicated for 1 h in a water
bath. The working electrode was prepared by drop casting of 10
μL ink onto a glassy carbon electrode (0.4−0.5 mg cm−2
loading) followed by dropping 5 μL Nafion solution to fix the
electrocatalyst. The electrode was dried at room temperature
before electrochemical measurements. Electrochemical HER
activity and stability tests were carried out in a three electrode
cell configuration using a rotating disc electrode (RDE, PAR
Model 636 RDE) attached with a potentiostat (Ivium
Technologies). A Ag/AgCl (3.0 M NaCl) electrode and a Pt
wire were used as reference and counter electrodes,
respectively. All potentials were referenced to the reversible
hydrogen electrode (RHE) by the equation ERHE = E(Ag/AgCl) +
0.059 pH + 0.209.
The HER performance was measured in aqueous 0.5 M
H2SO4 (pH 0.3) and 1.0 M KOH (pH 14) at a scan rate of 5
mV s−1 at 1600 rpm after 20 cyclic voltammetry (CV) cycles in
the range of 0.4 to −0.3 VRHE. The electrochemical stability
tests were conducted by performing up to 2000 CV cycles in
the above potential ranges. Electrochemical impedance spec-
troscopy (EIS) was conducted in the same setup in the
frequency range of 100 kHz to 1 mHz with a modulation
amplitude of 10 mV. The EIS spectra were fitted by Z-view
software. For the electrochemical active surface area (ECSA) to
be evaluated, CV was conducted from 0.0 to 0.2 V (in 0.5 M
H2SO4) and −0.8 to −0.6 V (in 1.0 M KOH or NaOH) vs Ag/
AgCl with different sweep rates between 10 and 100 mV s−1.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acscatal.7b00555.
HER performance comparisons and curves, summary of
electrochemical data, XRD patterns, surface morpholo-
gies, SEM images, EDX-SEM images, EDS-STEM
images, XPS spectra depth profiles, ECSA calculations,
cyclic voltammograms, EIS data, and CV curves (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: jlee1234@unist.ac.kr.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This research was supported by the Basic Science Grant (NRF-
2015R1A2A1A10054346), Climate Change Response project
(2015M1A2A2074663), the Korea Center for Artificial Photo-
synthesis (KCAP, No. 2009-0093880) funded by MSIP, and
Project No. 10050509 funded by MOTIE of the Republic of
Korea.
■
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3038 DOI: 10.1021/acscatal.7b00555

ACS Catal. 2017, 7, 3030−3038