Letter

pubs.acs.org/NanoLett

Plasma-Assisted Synthesis of NiCoP for Efficient Overall Water

Splitting
Hanfeng Liang, Appala N. Gandi, Dalaver H. Anjum, Xianbin Wang, Udo Schwingenschlögl,
and Husam N. Alshareef*
Materials Science and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal23955-6900, Saudi Arabia
*
S Supporting Information
Downloaded via NATL INST TECHLGY TIRUCHIRAPPALLI on December 2, 2019 at 10:23:49 (UTC).

ABSTRACT: Efficient water splitting requires highly active,

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earth-abundant, and robust catalysts. Monometallic phos-

phides such as Ni2P have been shown to be active toward
water splitting. Our theoretical analysis has suggested that their
performance can be further enhanced by substitution with
extrinsic metals, though very little work has been conducted in
this area. Here we present for the first time a novel PH3
plasma-assisted approach to convert NiCo hydroxides into ternary NiCoP. The obtained NiCoP nanostructure supported on Ni
foam shows superior catalytic activity toward the hydrogen evolution reaction (HER) with a low overpotential of 32 mV at −10
mA cm−2 in alkaline media. Moreover, it is also capable of catalyzing the oxygen evolution reaction (OER) with high efficiency
though the real active sites are surface oxides in situ formed during the catalysis. Specifically, a current density of 10 mA cm−2 is
achieved at overpotential of 280 mV. These overpotentials are among the best reported values for non-noble metal catalysts.
Most importantly, when used as both the cathode and anode for overall water splitting, a current density of 10 mA cm−2 is
achieved at a cell voltage as low as 1.58 V, making NiCoP among the most efficient earth-abundant catalysts for water splitting.
Moreover, our new synthetic approach can serve as a versatile route to synthesize various bimetallic or even more complex
phosphides for various applications.
KEYWORDS: NiCoP, plasma synthesis, DFT, HER, OER, electrocatalysis

M olecular hydrogen (H2) is a clean and sustainable energy

carrier that has the potential to meet the ever-growing
global energy demands at no environmental cost.1,2 Water
splitting is one of the most promising ways to produce
hydrogen but it is a thermodynamically uphill reaction and thus
requires external energies such as electricity to initiate the
reaction. The water electrolysis can be promoted by highly
efficient and robust catalysts that can substantially expedite the
sluggish kinetics of the two half reactions, namely the hydrogen
evolution and the oxygen evolution reactions (HER and
OER).3−6 Precious metal-containing compounds are at present
the state-of-the-art catalysts (Pt for HER, whereas RuO2 and
IrO2 for OER) but their large-scale application is seriously
limited by the high cost and scarcity. Motivated by this
challenge, enormous efforts have been devoted to developing
cost-efficient alternatives including sulfides, selenides, phos-
phides, and many other nonprecious transition metal
compounds.3−6
Among them, metal phosphides such as Ni2P, CoP, MoP,
and WP have recently attracted extensive research interest
owing to their high activity.7−16 These compounds are well-
known hydrodesulfurization (HDS) catalysts and recently have
demonstrated their efficacy for HER catalysis, which is not
surprising because both the HDS and HER rely on the
reversible adsorption and desorption of hydrogen on the
catalyst surface.15,17−20 In HDS, the hydrogen dissociates and
then reacts with sulfur to form H2S, whereas in HER, protons
bind to the catalyst to produce H2.19,21,22 Ni2P has shown the
best activity toward the HDS among the monometallic
phosphides and other compounds; recent efforts have been
directed toward further enhancing its performance by
substituting other transition metals such as Mo and Co.23−25
This is because a synergistic effect between these components
was foreseen as already confirmed for bimetallic sulfides.
Unexpectedly, however, the bimetallic phosphides did not show
superior activity to the monometallic phosphides expect for the
case of NixCoyP where a 50% increase in conversion was
achieved.26 Given the commonalities between the HDS and
HER, we predicted that the Co substitution would also enhance
the HER activity of Ni2P. We noticed that it has been
previously demonstrated by Jin et al. that the substitution of
one S atom of CoS2 with P atom could alter the electronic
structure and consequently dramatically enhance the HER
performance.27 In fact, the resultant CoPS is currently the best
non-noble metal HER catalyst in acidic media. We hence
carried out density function theory (DFT) calculations to
determine if the Co substitution influences the electronic
structure of Ni2P and the surface adsorption energy of the
reactants and thus the HER activity. Both the Ni2P and NiCoP
adopt the hexagonal Fe2P structure (see Figure 1a,b, and also
Received: September 9, 2016
Revised: October 19, 2016
Published: November 9, 2016

© 2016 American Chemical Society 7718 DOI: 10.1021/acs.nanolett.6b03803

Nano Lett. 2016, 16, 7718−7725
Nano Letters Letter

Figure 1. Crystal structures and theoretical predictions of the properties of Ni2P and NiCoP. (a,b) Crystal structures in unit cell of Ni2P and NiCoP.
(c,d) Electronic band structures and projected densities of states of the bulk Ni2P and NiCoP (spin-up, green curves; spin-down, red curves),
respectively. (e) Free-energy diagram for H adsorption on the Ni2P, NiCoP (0001) and Pt(111) surfaces. (f) Adsorption energy for H2O.

Figure 2. Synthetic route and structural characterization of the NiCoP nanostructure. (a) Schematic illustration of the synthetic route for NiCoP
nanostructure on Ni foam. (b) PXRD patterns of NiCo−OH and the converted NiCoP. The asterisks mark the diffraction peaks from Ni foam. (c)
SEM image of NiCo−OH. (d) SEM images and (e) corresponding EDS elemental maps of the NiCoP. (f,g) TEM images, (h) SAED pattern, and
(i) high-resolution TEM image and EDS spectrum (inset) of the NiCoP. The dashed white line highlights the crystalline−amorphous boundary.

7719 DOI: 10.1021/acs.nanolett.6b03803

Nano Lett. 2016, 16, 7718−7725
Nano Letters
Figure 3. XPS characterization of the NiCo−OH precursor and the NiCoP. (a) Ni 2p3/2 spectra, and (b) Co 2p3/2 spectra of the NiCo−OH
precursor and the NiCoP. (c) P 2p spectrum of the NiCoP. Circles, raw data; gray lines, background; yellow lines, overall fit; and other colored lines,
fit components.
Figure S2 in Supporting Information). As demonstrated in
Figure 1c,d, Ni2P and NiCoP show no band gap, that is, a
metallic nature, which would favor the electron transfer in
catalysis. The d-states of NiCoP are found closer to the Fermi
level as compared to Ni2P, which points to a lower intermedia
adsorption energy. The HER pathway in acidic media is
generally depicted as three-state diagram with initial state of H+
+ e, intermediate adsorbed H* (* being the adsorption site),
and product of 1/2H2.28,29 The Gibbs free energy of the
adsorbed H*, |ΔGH*|, is commonly used to evaluate the HER
activity of catalysts.28,29 We thus calculated the Gibbs free
energy for H adsorption (ΔGH*) on the (0001) surface of Ni2P
and NiCoP (see Supporting Information for calculation
details). Because the HER relies on the reversible adsorption
and desorption of H, ideally the H binding should be neither
too strong nor too weak, that is, |ΔGH*| should be close to
thermo-neutral (|ΔGH*| = 0).29 According to Figure 1e, ΔGH*
of the Ni2P (0001) surface is −0.86 and −0.45 eV for sites 1
and 2, respectively, see the adsorption sites in Figure S3. Co
substitution lowers the ΔGH* on the NiCoP (0001) surface
dramatically to −0.15 (site 1) and −0.14 eV (site 2), which are
close to the value on the Pt(111) surface. Note that the HER in
alkaline media requires an additional first step of water
dissociation;3 we thus further calculated the adsorption energy
of an H2O molecule (ΔEH2O) on the Ni2P and NiCoP (0001)
surfaces and found in both cases values (absolute value) of
more than 18 eV, indicating strong ability of water adsorption
(Figure 1f). In fact, the adsorption of water is much more
favorable on NiCoP (0001) surface than that on Pt(111)
surface, which possesses an absolute adsorption energy of 8.97
eV. Therefore, the DFT result suggests that the NiCoP is
indeed a highly active HER catalyst in alkaline media.
Besides the HER, the other half reaction of water splitting,
namely OER, is also of key importance. In fact, the OER has
long been the bottleneck because of its sluggish kinetics.
Efficient water splitting requires the optimization of both the
HER and OER catalysts.3 Ideally, the water splitting should be
driven by the same catalyst, which would greatly simplify the
water splitting system and make water electrolysis feasible at
the industrial scale. Interestingly, some monometallic phos-
phides such as Ni2P and CoP have recently been reported to
act as OER catalysts.7,8,30,31 Given the synergistic effect
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between Ni and Co during OER,32,33 as well as the metallic
nature and strong ability of water adsorption on NiCoP, one
can expect that the NiCoP could potentially serve as an efficient
OER catalyst (through the real active sites for OER are metal
oxides as demonstrated later). Motivated by these promising
predictions, we set out to design and synthesize a bimetallic
phosphide phase, namely NiCoP, and further establish it as a
cost-efficient and highly active electrocatalyst for both the HER
and OER in alkaline media. The NiCoP supported on Ni foam
(NiCoP/NF) was synthesized using a novel PH3 plasma-
assisted process and the resulting electrodes achieved stable
performance for both the HER and OER that are superior to
most of the catalysts reported so far. Furthermore, the NiCoP/
NF is also capable of catalyzing overall water splitting with a
cell voltage as low as 1.58 V at the current density of 10 mA
cm−2 and outstanding long-term durability.
The NiCoP nanostructure supported on Ni foam was
converted from hydrothermally formed NiCo hydroxide
(NiCo−OH) precursor using a novel PH3 plasma-assisted
process as illustrated in Figure 2a (see Supporting Information
for details). Compared to conventional synthetic methods for
phosphides,13 our newly developed plasma-assisted process
enables low temperature, fast preparation and could be, in
principle, applied to synthesize various metal phosphides. Most
importantly, because of the high reactivity of plasma we can
even directly convert metals such as Cu into Cu3P using this
unique technique at a relatively low temperature (Figure S4),
which is otherwise much more difficult to synthesize through
commonly practiced methods. Note that for the synthesis of
NiCoP, the temperature was set at 250 °C to avoid the
phosphorization of Ni foam, which occurs at 300 °C (Figure
S4). We first characterized the crystal structure and the
morphology of the NiCoP. The powder X-ray diffraction
(PXRD) patterns (Figure 2b) clearly suggest that the NiCo−
OH precursor was converted into hexagonal NiCoP (space
group P6̅2m, a = 5.834 Å), further confirming the efficacy of
converting hydroxides to phosphides by PH3 plasma treatment.
The scanning electron microscopy (SEM) image shows that the
NiCo−OH (Figure 2c) is composed of many nanoplates, a
typical morphology for hydroxides. These nanoplates are grown
uniformly on the Ni foam and are interconnected with each
other, forming a wall-like structure. This morphology is largely
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Nano Letters Letter

Figure 4. Hydrogen evolution reaction electrocatalysis in 1 M KOH. (a) IR-corrected polarization curves per geometric area of the NiCoP/NF
recorded at a scan rate of 3 mV s−1, along with Ni2P/NF, NiCo−OH/NF, and NF for comparison. (b) Polarization curves-derived Tafel slopes for
the corresponding electrocatalysts. (c) Long-term stability test carried out under a constant current density of −10 mA cm−2. (d) Difference in
current density plotted against scan rate showing the extraction of the double-layer capacitances. (e) Polarization curves from (a) normalized to the
electrochemical active surface area (ECSA). (f) The H2 turn over frequencies (TOFs) per surface site over different catalysts.

retained after the phosphorization. As shown in Figure 2d, the
NiCoP exhibits a hierarchical structure with thin nanoplates
lying aslant or perpendicular to the substrate. Such highly open
network could possibly have good mechanical strength and
enable a close contact with the electrolyte, which is believed to
be beneficial for electrocatalysis.32,34 The energy dispersive X-
ray spectroscopy (EDS) mapping (Figure 2e) confirms the
presence of Ni, Co, and P elements. The ratio of Ni/Co/P was
determined to be 1.106:1:1.138, giving a stoichiometric formula
of Ni1.11CoP1.14, close to that of NiCoP. The atomic
distribution of Ni, Co, and P is further revealed by the
scanning transmission electron microscopy-electron energy loss
spectroscopy (STEM-EELS) elemental mapping (Figure S5).
Though the overall morphology barely changes, the TEM
image reveals that many pores are distributed uniformly
throughout the NiCoP (Figure 2f) upon phosphorization. A
close observation (Figure 2g) further shows the NiCoP plate is
composed of numerous small nanocrystallites. The polycrystal-
line nature is further evidenced by the corresponding selected
area electron diffraction (SAED) pattern (Figure 2h), which
can be indexed into hexagonal NiCoP, consistent with the
PXRD result. We then performed high-resolution TEM
(HRTEM) to examine the nanostructure in more detail. As
shown in Figure 2i, small crystalline NiCoP nanoparticles are
surrounded by amorphous-like shells (∼2 nm), suggesting the
surface of NiCoP may be oxidized to form phosphates due to
air contact. This explains the high amount of O detected by
EDS (inset of Figure 2i; the Cu and C come from TEM grid).
Such crystalline−amorphous structure could protect the inner
NiCoP from being etched to some degree during the catalysis
and more importantly would promote the electron transfer
from the metallic inner NiCoP to the outer shell and thus
improve the catalytic activity. For comparison, we also
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synthesized Ni2P with similar platelike porous nanostructure
using Ni(OH)2 as precursor. The synthesis and detailed
structural characterization (Figure S6) can be found in
Supporting Information.
We further carried out the X-ray photoelectron spectroscopy
(XPS) measurements to probe the surface composition and the
oxidation state of the NiCoP. The Ni 2p3/2 core level spectrum
(Figure 3a) of NiCo−OH shows two main peaks at binding
energies of 855.6 and 861.1 eV that can be assigned to
Ni(OH)x and its satellite peak.35 After phosphorization, three
peaks with binding energies of 853.0, 856.3, and 861.1 eV are
observed, which should be related to the Ni−P, Ni−POx, and
the satellite peak, respectively. Note that the binding energy of
853.0 is very close to that of metallic Ni (852.6 eV),36
suggesting the presence of partially charged Ni species (Niδ+, δ
is likely close to 0). Similarly, the Co 2p3/2 segment of the
converted NiCoP (Figure 3b) possesses a new peak located at
778.5 eV as a consequence of the formation of Co−P.20,31 This
binding energy is also found to be slightly higher than that of
metallic Co (778.2 eV),37 indicating that the Co carries a
partially positive charge (Coδ+). The peak at 781.5 eV could be
ascribed to a Co oxidation state, which is associated with Co−
POx.31Figure 3c shows the P 2p region, where two doublets
with main peak binding energies at 129.1 and 132.9 eV are
observed. The former can be assigned to reduced phosphorus
in the form of metal phosphides, and the latter to phosphate
species (P5+).31,38 The binding energy of 129.3 eV is slightly
lower than that of elemental P (130.0 eV),39 which suggests the
P is partially negatively charged (Pδ‑). Thus, the P can act as
base to trap positively charged protons during electrocatalysis.
This feature is similar to those observed in [NiFe] hydro-
genase,19 which is a highly active biological HER catalyst. The
XPS result further confirms the formation of NiCoP with
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Figure 5. Oxygen evolution reaction electrocatalysis in 1 M KOH. (a) IR-corrected polarization curves per geometric area of the NiCo-P/NF
recorded at a low scan rate of 0.5 mV s−1, along with Ni−P/NF, NiCo−OH/NF, and NF for comparison. (b) Polarization curves-derived Tafel
slopes for the corresponding electrocatalysts. (c) Long-term stability test carried out at a constant current density of 10 mA cm−2. (d) Plots showing
the extraction of the double-layer capacitances allows the estimation of the electrochemically active surface area. (e) Polarization curves from (a)
normalized to the ECSA. (f) The O2 turn over frequencies (TOFs) per surface site over different catalysts.

surface partially being oxidized to phosphate as observed from
TEM analysis. We also performed XPS analysis on Ni2P
(Figure S7). Compared to Ni2P, the Ni 2p3/2 and P 2p peaks of
NiCoP slightly shift toward the lower binding energies,
indicating a change in the electronic structure occurs due to
Co substitution.
We then compared the HER performance of the NiCoP,
Ni2P and NiCo−OH using a standard three-electrode cell in 1
M KOH (see Supporting Information for details). The
comparison in Figure 4a shows that the NiCoP/NF exhibits
a much higher activity than Ni2P/NF and NiCo−OH/NF.
Specifically, a geometric current density of −10 mA cm−2 can
be achieved at overpotential as low as 32 mV on NiCoP/NF
(see the original data and the Nyquist plots in Figure S8). In
contrast, 93, 201, and 242 mV overpotentials are required for
Ni2P/NF, NiCo−OH/NF, and bare NF to drive the same
current density, respectively. Note the bare NF only shows
negligible current in the potential window of −200 to 0 mV
versus the reversible hydrogen electrode (RHE), further
supporting the high performance of NiCoP. The NiCoP/NF
also shows a smallest Tafel slope of 37 mV dec−1 among the
four catalysts investigated (Figure 4b). Such Tafel slope value
suggests a two-electron transfer process occurs upon NiCoP/
NF following the Volmer−Tafel mechanism.40 Furthermore, an
exchange current density (J0) as high as 1.36 mA cm−2 was
obtained for NiCoP/NF based on the intercept of the Tafel
plot, which is much larger than that of Ni2P/NF (0.37 mA
cm−2). These catalysts were also found highly stable over a 24 h
long-term test (Figure 4c). Poststructural characterization
(Figure S9) shows that the overall platelike morphology of
the NiCoP does not change significantly, and the major phase
remains NiCoP as confirmed by the HRTEM. Nevertheless, a
thin layer was formed on the surface of the NiCoP plate. EELS
7722
mapping suggests that this thin layer consists of Ni, Co, and O
elements, while no P was detected. XPS (Figure S10) on the
NiCoP after HER further reveals the disappearance of the low
energy peaks of Ni (853.0 eV), Co (778.5 eV), and P (129.3
eV). These observations indicate the surface of the NiCoP is
dominated by NixCoy(OH) after the HER catalysis. Similar
phenomenon has been observed for Ni phosphides (Ni5P4/
Ni2P/NiP2), where the formation of amorphous Ni(OH)x was
observed after the HER catalysis in alkaline media.41 To gain
insights into the intrinsic activity of the catalysts, we measured
the double-layer capacitances (Cdl) to estimate the electro-
catalytic active surface areas (ECSAs)42,43 and further
normalized the geometric current density to the corresponding
ECSA (see Supporting Information for details). As shown in
Figure 4d, the NiCoP/NF has the biggest Cdl, thus the highest
catalytically relevant surface area, which could be mainly
attributed to the porous structure and more exposed active
sites. When normalized to the ECSA (Figure 4e), the NiCoP/
NF displays the highest current density, followed by Ni2P and
then NiCo−OH, indicating the NiCoP is intrinsically more
active than Ni2P. We also calculated the H2 turn over
frequencies (TOFs) per surface site for these catalysts to
further evaluate their intrinsic HER activity. Here we assume all
surface sites (including both the transition metal and P atoms)
are involved in the HER, which would give a lower limit of the
TOF (see Supporting Information for details). Figure 4f shows
the calculated TOFs plotted against potential. The average
TOF for NiCoP/NF is almost 2 and 13 times larger than those
for Ni2P/NF and NiCo−OH/NF. For instance, the exper-
imental TOFs are 8.93, 3.48, and 0.64 s−1 for NiCoP/NF,
Ni2P/NF, and NiCo−OH/NF at −100 mV versus RHE,
respectively. These observations confirm the predictions from
DFT and establish our NiCoP/NF as an outstanding HER
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Nano Letters
catalyst that outperforms almost all the reported earth-
abundant HER catalysts in alkaline media (see comparison in
Table S1) and further proves the efficacy of our strategy to
significantly enhance the HER performance of Ni2P by tuning
the electronic structure and the hydrogen adsorption energy
through Co substitution.
We further investigated the OER performance of the
NiCoP/NF in 1 M KOH, along with Ni2P/NF and NiCo−
OH/NF for comparison (see Supporting Information for
details). Figure 5a shows the IR-corrected linear sweep
voltammetry (LSV) curves (see uncorrected data and the
Nyquist plots in Figure S11). The NiCoP/NF exhibits the
highest OER activity and can deliver a geometric current
density of 10 mA cm−2 at an overpotential of 280 mV. In
contrast, Ni2P/NF and NiCo−OH/NF require overpotentials
of 340 and 404 mV to drive the same current density,
respectively. Furthermore, the current density obtained for
NiCoP/NF at overpotential of 300 mV is 16.5 mA cm−2, which
is 3 times larger than that for Ni2P/NF (4.23 mA cm−2). These
numbers compare favorably to many other recently reported
high-performance OER catalysts (Table S2) and place the
NiCoP/NF among the top tier of earth-abundant OER
catalysts. All catalysts show a distinct anodic peak between
1.3 and 1.5 V versus RHE, which should be associated with the
oxidation of Ni or Co (or both) species.33 For Ni2P/NF, this
anodic peak is located at around ∼1.4 V versus RHE, which is
in agreement with the reported value for Ni2P/NF.38
Interestingly, such anodic peak observed for NiCoP/NF shifts
to lower potential (∼1.35 V versus RHE), suggesting that the
electronic structure of Ni2P is likely altered by the presence of
Co ions. The Co substitution may lower the thermodynamic
barrier of the proton-coupled electron transfer (PCET) pre-
equilibrium and promote the O−O bond formation, thus
lowering the activation barrier required for OER, and leading to
enhanced catalytic performance.44 The Tafel slopes of these
catalysts are found to be very close (Figure 5b), suggesting
similar OER kinetics. The stability of these materials was
examined by chronopotentiometry and the result shows these
catalysts are reasonably stable (Figure 5c). For NiCoP/NF, the
potential required to maintain a constant geometric current
density of 10 mA cm−2 only slightly increases from 1.51 to 1.53
V versus RHE after 24 h. The overall morphology of the NiCoP
plates is also maintained after the OER catalysis (Figure S12).
The improved performance of NiCoP might be attributed to
the synergistic effect between Ni and Co,32,33 and the increase
in ECSA as revealed by the double-layer capacitance measure-
ments (Figure 5d). The Cdl of NiCoP/NF (4.9 mF cm−2) is
about 1.5 times as large as that of the Ni2P/NF (3.2 mF cm−2),
suggesting more accessible active sites are exposed. The
geometric current densities were then normalized to ECSA in
order to compare the intrinsic activity of these catalysts. As
shown in Figure 5e, the NiCoP/NF again shows the highest
normalized current densities at lower overpotential. Further-
more, the calculated TOF (Figure 5f) of the NiCoP/NF at
overpotential of 300 mV (1.53 V versus RHE) is 3.88 s−1, more
than twice as that of the Ni2P/NF (1.54 s−1). These results
confirm the higher intrinsic catalytic activity of NiCoP than
Ni2P and the potential of the NiCoP/NF as a cost-efficient and
highly active alternative for OER.
We noted that the ECSAs of the NiCoP/NF during HER
and OER are significantly different, whereas the active sites for
HER and OER are not necessarily the same; this is more likely
an indication of the surface composition change during the two
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reactions. In fact, the real surface active sites of metal
phosphides for OER have recently demonstrated to be the
metal oxyhydroxides (or oxides) in situ formed during the
OER,7,8,30 which are different from those for HER. We thus
carried out the XPS measurements to further understand the
compositional change after the OER catalysis (Figure S10).
After OER catalysis, the low-valent Ni (853.0 eV) and Co
(778.5 eV) peaks, which are assigned to Ni−P and Co−P in the
as-synthesized sample, disappear, and the P signal becomes very
weak and is actually below the detection limit of XPS. This
result suggests that the surface-bound phosphates and
phosphides are being oxidized to oxides or oxyhydroxides, as
commonly observed for metal phosphides after OER
catalysis.41 Of note, a P-deficient surface layer can be clearly
identified by the STEM-EELS mapping (Figure S12). The
resulting NiCoP/NixCoyO (or NixCoyOOH) heterojunction
could promote the electron transfer from the metallic NiCoP to
the surface layer and thus contribute to the OER activity, as
suggested by a previous study on OER over Ni phosphides.41
Encouraged by the high catalytic activity of the NiCoP/NF
toward both the HER and OER in alkaline media, we further
used the NiCoP/NF as both the anode and cathode for water
electrolysis in a single electrolyzer (Figure 6a). Figure 6b shows
Figure 6. NiCoP/NF electrocatalyst for overall water splitting in 1 M
KOH. (a) Schematic illustration of two-electrode cell using NiCoP/
NF for both anode and cathode for water splitting. (b) Polarization
curve recorded at 0.5 mV s−1. Inset: digital photograph of the two-
electrode configuration. (c) Long-term stability test carried out at
constant current densities of 10, 20, and 50 mA cm−2.
the polarization curve recorded at 0.5 mV s−1. Remarkably, the
current density of 10 mA cm−2 can be achieved at a cell voltage
as low as 1.58 V, and 100 and 200 mA cm−2 at 1.82 and 1.98 V,
respectively. These numbers are better than or at least
comparable to previously reported transition metal phosphide,
chalcogenide, and hydroxide-based electrocatalysts (Table S3).
Furthermore, the NiCoP/NF shows very good stability upon
long-term testing and only a slight deactivation is observed after
24 h (Figure 6c).
The excellent catalytic activity of the NiCoP/NF could be
attributed to the following factors: (i) The Co substitution
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alters the electronic structure and further optimizes the
reversible adsorption and desorption of hydrogen (Figure
1c). (ii) The metallic nature of the NiCoP/NF ensures good
electric conductivity thus favors fast electron transport (Figure
1b). For comparison, the annealed product (see Supporting
Information for synthetic details), namely NiCo oxides/NF,
shows inferior performance for both the HER and OER (Figure
S13), which is likely due to the poor intrinsic electric
conductivity of oxides. (iii) The fast synthesized NiCoP
nanocrystals were found rich of defects (Figure S14), which
promote the electrocatalytic activity.45 (iv) The nanopores
generate abundant active sites, leading to improved catalytic
activity per geometric area. (v) The porous structure enables
close contact with electrolyte thus allows more efficient
utilization of active site. (vi) The highly open hierarchical
structure facilitates the gas release during the HER and OER
catalysis. (vii) The direct integration of NiCoP onto Ni foam
not only enables good mechanical adhesion and electric
connection but also avoids the use of extra binders. (vii) The
Ni foam support also contributes to the catalysis to some
degree.
In conclusion, we present a combined theoretical and
experimental study to establish NiCoP as a highly active and
earth-abundant electrocatalyst for water splitting. The NiCoP
was synthesized using a novel PH3 plasma-assisted method,
which in principle could serve as a versatile route to synthesize
various bimetallic or even more complex phosphides. The as-
synthesized NiCoP porous nanostructures supported on Ni
foam achieved superior performance for both the HER and
OER (note that the real active sites for OER are NiCoP-derived
oxides) in alkaline media than reported metal phosphides and
are among the most active earth-abundant electrocatalysts
developed so far. Our result suggests that substituting a second
metal into monometallic phosphides could effectively alter the
electronic structure of the parent compounds and further tune
the hydrogen (or water) adsorption energy, thus dramatically
enhance the catalytic activity. This strategy might be generally
applicable for enhancing the electrocatalytic and many other
applications (e.g., batteries, supercapacitors) of transition metal
phosphides.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.nano-
lett.6b03803.
Experimental details, additional supporting data, and
comparison of catalytic performance (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: husam.alshareef@kaust.edu.sa.
ORCID
Husam N. Alshareef: 0000-0001-5029-2142
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The research reported in this publication was supported by
funding from King Abdullah University of Science and
Technology (KAUST).
7724
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7725 DOI: 10.1021/acs.nanolett.6b03803

Nano Lett. 2016, 16, 7718−7725