Research Article

Cite This: ACS Appl. Mater. Interfaces 2018, 10, 27712−27722 www.acsami.org

Cobalt Sulfide/Nickel Sulfide Heterostructure Directly Grown on

Nickel Foam: An Efficient and Durable Electrocatalyst for Overall
Water Splitting Application
Subhasis Shit,† Suman Chhetri,†,‡ Wooree Jang,§ Naresh C. Murmu,†,‡ Hyeyoung Koo,§
Pranab Samanta,†,‡ and Tapas Kuila*,†,‡
†
Surface Engineering & Tribology Division, Council of Scientific and Industrial Research-Central Mechanical Engineering Research
Institute, Durgapur 713209, India
‡
Academy of Scientific and Innovative Research (AcSIR), CSIR-CMERI Campus, Durgapur 713209, India
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§
Soft Innovative Materials Research Centre, Institute of Advanced Composite Materials, Korea Institute of Science and Technology
(KIST), Jeonbuk, Seoul 565905, South Korea
*
S Supporting Information

ABSTRACT: Fabrication of high-performance noble-metal-free bifunctional

electrocatalysts for both hydrogen evolution reaction (HER) and oxygen
evolution reaction (OER) in water is a promising strategy toward future
carbon-neutral economy. Herein, a one-pot hydrothermal synthesis of cobalt
sulfide/nickel sulfide heterostructure supported by nickel foam (CoSx/Ni3S2@
NF) was performed. The Ni foam acted as the three-dimensional conducting
substrate as well as the source of nickel for Ni3S2. The formation of CoSx/
Ni3S2@NF was confirmed by X-ray diffraction and X-ray photoelectron
spectroscopy. The formation of CoSx/Ni3S2@NF facilitated easy charge
transport and showed synergistic electrocatalytic effect toward HER, OER, and
overall water splitting in alkaline medium. Remarkably, CoSx/Ni3S2@NF
showed catalytic activity comparable with that of benchmarking electro-
catalysts Pt/C and RuO2. For CoSx/Ni3S2@NF, overpotentials of 204 and 280
mV were required to achieve current densities of 10 and 20 mA cm−2 for HER
and OER, respectively, in 1.0 M KOH solution. A two-electrode system was formulated for overall water splitting reaction,
which showed current densities of 10 and 50 mA cm−2 at 1.572 and 1.684 V, respectively. The prepared catalyst exhibited
excellent durability in HER and OER catalyzing conditions and also in overall water splitting operation. Therefore, CoSx/
Ni3S2@NF could be a promising noble-metal-free electrocatalyst for overall water splitting application.
KEYWORDS: hydrogen evolution reaction, oxygen evolution reaction, bifunctional electrocatalyst, overall water splitting,
heterostructure

1. INTRODUCTION Ir-based oxides.6,7 However, their low abundance, high cost,

The harness and storage of renewable energy are challenging and short-term durability impede their large-scale application
yet promising approach to confront with the two major as electrocatalysts.8,9 In addition, the efficiency of overall water
problems of contemporary timeenergy depletion and splitting depends on both HER and OER rate kinetics.
environmental degradation. Central to this challenge, hydrogen Therefore, the development of a material which can
has a great merit to be used as a clean energy carrier because it concurrently catalyze both the HER and OER in the same
has a high energy density of 283 kJ mol−1 and produces only electrolytic medium could be advantageous, which might
water (H2O) as a product after combustion.1 Therefore, further simplify the development process of an electrolyzer
electrochemical water splitting using energy derived from device.10−13
sources such as solar, wind, and so forth to produce hydrogen Over the last few years, extensive research is being carried
at the cathode and oxygen at the anode shows great out to develop earth-abundant, noble-metal-free bifunctional
commitment.2,3 However, both hydrogen evolution reaction electrocatalysts. Several materials such as transition-metal
(HER) and oxygen evolution reaction (OER) have sluggish chalcogenides, pnictides, borides, and so forth were developed
kinetics; thus, employment of an effective catalyst is necessary
to narrow the gap between theoretically calculated and Received: March 14, 2018
practically required potential.4,5 The state-of-the-art catalysts Accepted: July 25, 2018
used for HER are Pt-based materials and for OER are Ru- and Published: July 25, 2018

© 2018 American Chemical Society 27712 DOI: 10.1021/acsami.8b04223

ACS Appl. Mater. Interfaces 2018, 10, 27712−27722
ACS Applied Materials & Interfaces Research Article

as electrocatalysts for the water splitting reaction.14−22 rinsed thoroughly with distilled water. Thereafter, it was dried inside a
However, these types of materials suffer from low electrical vacuum oven at 60 °C for 12 h. The change in mass was determined
conductivity and less specific surface area. Direct growing of with the help of a high-precision balance, and the average mass
nanostructured catalyst materials on conducting substrates loading was ∼2.83 mg cm−2. Two other materials were prepared
according to the similar procedure where CoCl2·H2O was taken at an
such as carbon cloth, metal foam, metal mesh, metal foil, and amount of 0.05 and 0.2 mmol, which were denoted as C0.05NS and
so forth have proven effective in overcoming those C0.2NS, respectively.
lacunae.23−27 To the present, nickel sulfide has been For comparison, Ni3S2@NF was prepared according to the same
extensively studied and been proposed to be active toward procedure as mentioned earlier without using the cobalt precursor.
electrocatalytic water splitting in the alkaline medium,12,16,28 CoSx was also prepared following the same procedure without putting
but its catalytic activity toward HER is not up to the mark.11,13 NF in the hydrothermal reactor. After the preparation of CoSx, a
In order to augment the catalytic activity, Ni3S2 has been catalyst ink was prepared and loaded on to the pretreated NF to
hybridized with a highly efficient electrocatalyst, such as MoS2, fabricate CoSx@NF.
which exhibited improved catalytic activity.11,29,30 Although 2.2.2. Fabrication of Pt/C@NF and RuO2@NF. About 71 mg of Pt/
C (10 wt % Pt content) and RuO2 was taken in two different sample
MoS2 has good catalytic activity toward HER in the acidic tubes each containing ∼5 mL of N,N-dimethylformamide. As a binder
medium, its activity is not up to the mark in the alkaline material, ∼7 mg of polyvinylidene fluoride was added to each
medium.31 Prior studies revealed that sulfides of cobalt, such as dispersion. The catalyst inks were then sonicated for ∼30 min. After
Co9S8, CoS2, CoS, and so forth, have better catalytic activity that, the calculated amount of catalyst inks was deposited on two
toward both HER and OER in the alkaline medium and have precleaned NF pieces. The loading of the catalysts was ∼2.83 mg
excellent chemical stability and electrical conductivity.32−35 cm−2 in each case.
Furthermore, previous studies revealed that the free energy of 2.3. Physicochemical Characterizations. Field emission
adsorption of H- and O-containing species decreased with the scanning electron microscopy (FE-SEM) and energy-dispersive X-
incorporation of Co atoms on the edge sites of other ray spectroscopy (EDXS) assisted elemental mapping were performed
using Sigma HD, Carl Zeiss, Germany. High-resolution transmission
transition-metal chalcogenides. Moreover, the charge transfer electron microscopy (HR-TEM) images, selective area electron
within the electrocatalyst material via S-linkages as well as diffraction (SAED) pattern, and EDXS spectra were recorded at
between the electrocatalyst interface with H- and O-containing 200 kV using a JEM 2100 microscope, JEOL, Japan. The powder X-
species increased synergistically. As a consequence, the HER ray diffraction (PXRD) patterns were recorded using Cu Kα radiation
and OER catalyzing activity increased significantly.36−38 (λ = 0.15418 nm) by D2 PHASER, Bruker, Germany. X-ray
Therefore, integration of cobalt sulfide with nickel sulfide photoelectron spectroscopy (XPS) was carried out using Thermal
may be promising toward the electrocatalytic water splitting Scientific equipped with a monochromatic Al Kα X-ray source
application. (1486.6 eV).
Herein, cobalt sulfide-anchored nickel sulfide on nickel foam 2.4. Electrochemical Measurements. All the electrochemical
measurements were carried out using the PARSTAT 4000 (Princeton
(CoSx/Ni3S2@NF) was fabricated for the first time via a one- Applied Research, USA) electrochemical workstation. About 1.0 M
step hydrothermal process, using NF itself as the nickel KOH solution was used as the electrolyte throughout the experi-
precursor. The prepared CoSx/Ni3S2@NF electrode showed ments. In the three-electrode electrochemical system, catalyst-loaded
excellent performance as an electrocatalyst toward overall NFs, Pt wire, and Ag/AgCl/saturated KCl were used as working,
water splitting. It exhibited comparable catalytic activity with counter, and reference electrodes, respectively. The potentials
that of Pt- and Ru-based electrocatalysts used for HER and recorded were converted into reversible hydrogen electrode (RHE)
OER. Overpotentials of 204 and 280 mV were required to scale according to the following equation:
achieve current densities of 10 and 20 mA cm−2 for HER and E RHE = EAg/AgCl/Sat.KCl + 0.059pH + 0.197
OER, respectively, in 1.0 M KOH solution. In order to ensure (1)
its overall water splitting competency, a two-electrode system The current densities reported in this current work were
was constructed using CoSx/Ni3S2@NF as both cathode and normalized as per the geometric area.39 Prior to recording the
anode in 1.0 M KOH solution. polarization curves, for HER and OER, several voltammetric cycles
were performed at a scan rate of 100 mV s−1. The linear sweep
2. EXPERIMENTAL SECTION voltammetry (LSV) scans were performed at a scan rate of 5 mV s−1
to minimize the double-layer charging current. All the above data
2.1. Materials. CoCl2·6H2O, thiourea, KOH pellets, and HCl
were 100% iR corrected to eliminate the influence of uncompensated
(∼35%) were purchased from Merck Specialties Pvt. Ltd. (Mumbai),
resistance. The Tafel plot was derived from the LSV curves, and the
India. NF was bought from Shanghai Winfay New Material Co. Ltd.,
analysis was carried out according to the following equation:
China. Absolute ethanol (99.9%) was obtained from Honyon
International Inc., China. Pt on activated carbon (10 wt %) and η = a + b log j (2)
RuO2 were purchased from Sigma-Aldrich. The mentioned chemicals
were of analytical grade and thus used without further purification where η is the overpotential, j is the current density, and b is the Tafel
unless specifically mentioned. slope. η was calculated according to the following equations:
2.2. Preparation of the Electrocatalyst. 2.2.1. Synthesis of
CoSx/Ni3S2@NF, Ni3S2@NF, and CoSx@NF. NF was cut into three For HER, η = 0 − E RHE (3)
pieces with dimensions 2 × 3 cm2. These pieces were then cleaned
sequentially with HCl solution (3 M), ethanol, and distilled water by
water bath sonication to remove oxide layers. At first, 0.1 mmol of For OER, η = E RHE − 1.229 (4)
CoCl2·6H2O and 1 mmol of thiourea were dissolved in 40 mL of
The electrochemically active surface area (ECSA) and the
distilled water separately. Then, one piece of cleaned NF, Co(II)
roughness factor (RF) are calculated from the electrochemical
solution, and thiourea solution were transferred into a 100 mL Teflon-
double-layer capacitance (Cdl) value following the equations:
lined stainless steel autoclave reactor. The autoclave reactor was
locked properly and placed inside a preheated oven at 120 °C for 12 Cdl
h. After that, the autoclave reactor was cooled down to room ECSA =
temperature and the prepared CoSx/Ni3S2@NF was taken out and 40 μF cm−2 per cm 2ECSA (5)

27713 DOI: 10.1021/acsami.8b04223

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ECSA formed a highly ordered scaffold with a size in the submicron

RF =
geometric area of the electrode (6) level. It has been found that such a type of porous structure is
advantageous for HER and OER, as it renders easy access to
The capacitance of atomically smooth planar surface in 1.0 M KOH
electrolyte ranges from 20 to 60 μF cm−2. For calculation, the area-
the active surface area to reactive substrates.43 Figure 1b,c
normalized specific capacitance was taken to be 40 μF cm−2.39,40 To shows the micrograph of CoSx/Ni3S2@NF. It is discernible
obtain Cdl, cyclic voltammetry (CV) scans were performed between a from the micrograph that the cuboid shaped CoSx has
narrow potential window, with different scan rates (ν). Then, Δjν−1/2 vertically protruded from the porous Ni3S2 scaffold. It is likely
were plotted against ν1/2 to obtain the Cdl value. Here, halves of the that spatially well connected Ni3S2 assisted the homogeneous
difference between the anodic and cathodic current densities (ja and growth of CoSx particles. The thickness of protruded CoSx is in
jc) are denoted as Δj, that is the range of submicron. The firm embedment of cuboid-
ja − jc shaped CoSx (Figure 1d) on a porous Ni3S2 base might have
Δj = facilitated a better charge transfer among them, leading to
2 (7)
effective catalytic performance. The FE-SEM image suggested
In order to test the durability of the electrode, 500 CV scans at a that the growth of the cuboid-shaped CoSx initiated on the
scan rate of 100 mV s−1 were performed between both 0.00 to −0.35 porous scaffold of Ni3S2. It was observed that the porous
V and 1.23 to 1.58 V potential regions. Long-term stability in
operational condition was verified using chronoamperometric studies
network of Ni3S2 conserved even after the growth of cuboid
applying constant potentials after dipping the fabricated electrode CoSx particles, which must have played a crucial role in
deep inside the electrolyte. Electrochemical impedance spectroscopy electrolyte diffusion and gas release.
(EIS) was conducted in the potentiostatic mode between frequency FE-SEM images of C0.05NS showed crumpled sheet-like
ranging from 100 kHz to 100 mHz applying a sinusoidal alternating structures with a porous network of Ni3S2@NF (as shown in
current (ac) potential of 10 mV and dc biases. The obtained Nyquist Figure S1a). In the case of C0.2NS, it was seen that the cuboid-
plots were fitted with the Randles equivalent circuit using ZView shaped CoSx completely covered the porous network of
software (Scribner Associates Inc., USA). The overall water splitting Ni3S2@NF (as shown in Figure S1b). As the exposed network
performances of the materials were tested in the two-electrode system of Ni3S2@NF was almost blocked, the access of ions to Ni sites
using symmetric electrodes as the cathode and anode in 1.0 M KOH
solution.
became difficult. For efficient catalysis, easy movement of ions
toward the catalytic sites is pertinent; thus, it well corroborates
3. RESULTS AND DISCUSSION with the decreased performance of the catalyst toward water
splitting.
3.1. Physicochemical Analysis. In order to understand The gray-colored NF turned black when CoSx/Ni3S2@NF
how the sulfides of Ni and Co are attached onto the surface of was formed after the hydrothermal reaction, whereas Ni3S2@
the NF, the FE-SEM image was analyzed. The three- NF appeared brownish in color (Figure S2). The correspond-
dimensional structured porous NF was extensively used as a ing elemental mapping for CoSx/Ni3S2@NF sample was
substrate to fabricate electrocatalysts for HER and OER in the carried out, and it is presented in Figure 2. The elemental
alkaline electrolyte medium.41,42 One of the advantages of
using the NF as a catalyst template is that the prospective
catalyst can be directly grown and anchored on its surface
without the use of a binder for immobilizing the catalyst. The
current study is an effort to fabricate an effective catalyst by
growing and anchoring sulfides of Ni and Co on the NF
surface. In order to have a holistic knowledge of morphology
and homogeneity of the prepared heterostructure, first, the FE-
SEM image of Ni3S2 was analyzed and is presented in Figure 1.
On the sulfurization of NF, a uniform interconnected network
of Ni3S2 was formed (Figure 1a). The vertically grown Ni3S2

Figure 2. Elemental mapping images of CoSx/Ni3S2@NF: (a) Ni

(green), (b) Co (white), and (c) S (red) and (d) merged mappings of
Ni, Co, and S.

mapping images of Ni, Co, and S are presented as points with

green (Figure 2a), white (Figure 2b), and red (Figure 2c)
colors, respectively. The point mappings of all the individual
elements were merged and presented in a single two-
dimensional image as shown in Figure 2d. Therefore, the
mapping results confirmed that the constituting elements Ni,
Figure 1. (a) FE-SEM images of (a) Ni3S2@NF, (b,c) CoSx/Ni3S2@ Co, and S were homogeneously distributed throughout the
NF, and (d) cuboid-shaped CoSx formed in CoSx/Ni3S2@NF. CoSx/Ni3S2@NF sample.
27714 DOI: 10.1021/acsami.8b04223
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To further study the structural and morphological features, observed (R1).44 Furthermore, the interplanar distances of
the HR-TEM images as depicted in Figure 3a,b were (200) and (111) planes of CoS2 were found to be 0.28 and
0.32 nm, respectively, as indicated by R2 and R3 in Figure 3.45
Both CoS and CoS2 were observed to be present in the surface
region. The (101) and (110) planes of Ni3S2 were found to be
present with interplanar distances of 0.40 and 0.28 nm,
respectively (R4).46,47 The angle between these (110) and
(101) planes was measured to be ∼60°. Along with the above-
mentioned lattice fringes, some surplus fringes with different
spacing were also observed, which could be due to the
formation of a small amount of amorphous NiSx.
The SAED pattern image of CoSx/Ni3S2@NF (Figure 3c,d)
was found to contain fewer bright spots, which suggested
polycrystallinity or poor crystallinity. This might be due to the
presence of two kinds of moieties. Moreover, the EDXS
spectrum (Figure S3) confirmed the presence of Ni, Co, and S
in CoSx/Ni3S2@NF.
After scratching off some materials from the electrodes, the
PXRD patterns (shown in Figure 4a) had been recorded and
investigated. The peaks at 2θ values of 45, 52.4, and 77°
appeared because of the presence of metallic nickel (JCPDS
no. 65-2865).30 The peaks located at 2θ ≈ 22.5, 31.8, 38.45,
50.53, and 56° could be indexed to the (101), (110), (003),
(113), and (122) planes of Ni3S2 (JCPDS no. 44-1418),
respectively.46 Thus, the formation of Ni3S2 was confirmed in
Figure 3. (a,b) HR-TEM images and (c,d) SAED patterns of CoSx/ both the cases. Along with the above-mentioned peaks, some
Ni3S2@NF.
less prominent peaks also appeared in the PXRD spectrum of
the cobalt-containing electrocatalyst. The peaks located at 2θ
examined. The distances between the lattice fringes were ≈ 30.5, 34.56, 47.79, and 73.62° appeared because of the
calculated from the fast Fourier transformation at various diffraction from the (100), (101), (102), and (202) planes of
regions (indicated as R1, R2, R3, and R4). The presence of the hexagonal CoS phase (JCPDS no. 75-0605), respectively.48
CoS(101) planes with a lattice spacing of 0.25 nm were Two other small peaks at 2θ ≈ 32.88 and 40.35° were

Figure 4. (a) PXRD patterns of CoSx/Ni3S2@NF, CoSx, and Ni3S2@NF [“β” denotes Ni3S2 peaks (JCPDS no. 44-1418), “γ” denotes CoS peaks
(JCPDS no. 75-0605), and “ψ” denotes CoS2 peaks (JCPDS no. 41-1471)] and high-resolution XPS profiles of (b) Ni 2p, (c) Co 2p, and (d) S 2p
of CoSx/Ni3S2@NF.

27715 DOI: 10.1021/acsami.8b04223

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Figure 5. (a) HER polarization curves of CoSx/Ni3S2@NF, Ni3S2@NF, CoSx@NF, bare NF, and Pt/C@NF in 1.0 M KOH (with iR correction);
(b) corresponding Tafel plots; and (c) Nyquist plots of CoSx/Ni3S2@NF, CoSx@NF, Ni3S2@NF, and bare NF at an overpotential of 200 mV.

identified as Bragg diffraction peaks of (200) and (211) planes confirmed good electronic interactions between CoSx and
of CoS 2 (JCPDS no. 41-1471), respectively. 44 These Ni3S2.
observations confirmed the formation of amorphous CoSx on 3.2. Electrochemical Hydrogen Evolution Activity.
Ni3S2. When the PXRD pattern was recorded in the case of The electrocatalytic activity of CoSx/Ni3S2@NF toward HER
prepared CoSx, the peaks related to (111), (200), and (211) was studied in 1.0 M KOH solution in a three-electrode setup.
Bragg planes of CoS2 were observed.45 Along with them, a For comparison, a similar experiment was carried out for Pt/
peak with lesser intensity was observed, which was indexed to C@NF, CoSx@NF, Ni3S2@NF, and bare NF. Figure 5a
the (101) plane of CoS.48 depicts the obtained polarization curves for CoSx/Ni3S2@NF,
XPS was used to characterize the valance state of the Ni3S2@NF, CoSx@NF, bare NF, and Pt/C@NF. As expected,
constituting elements in CoSx/Ni3S2@NF. The deconvoluted Pt/C@NF showed a superior catalytic activity toward HER,
spectra of Ni 2p showed two strong peaks at 856.32 and which exhibited a benchmarking current density of 10 mA
873.88 eV, which were indexed to the Ni 2p3/2 and Ni 2p1/2 cm−2 at an overpotential of 139 mV. Nevertheless, a slight
peaks, respectively (Figure 4b). These peaks emerged because decrease in the catalytic activity of Pt/C was observed, which
of the presence of Ni2+ and Ni3+ in Ni3S2.30 Along with these, might be due to the low Pt percentage and use of a polymeric
two satellite peaks (indicated as “Sat.”) also appeared at 861.59 binder (see Figures S5 and S6). CoSx/Ni3S2@NF achieved a
and 879.91 eV. The 853 eV peak was identified to be the current density of 10 mA cm−2 at an overpotential (η10) of 204
mV, which is better than or comparable with some of the
characteristic peak of Ni3S2.46,49 For comparison, the Ni 2p
recently reported non-noble metal-based electrocatalysts (as
spectra of Ni3S2@NF (see Figure S4a) were investigated, and it
shown in Table S2). CoSx@NF and Ni3S2@NF achieved a
was observed that all the peaks in the Ni 2p spectra of CoSx/
current density of 10 mA cm−2 at overpotentials of 240 and
Ni3S2@NF were blue shifted, which indicated charge 269 mV, respectively, which indicated that the catalytic
redistribution between the interfaces of CoSx and Ni3S2.11,29 performance augmented after impregnation of CoSx in Ni3S2
In the deconvoluted XPS spectra of Co 2p, two strong peaks scaffold. Bare NF exhibited the least activity toward HER, as it
were observed at 781.79 and 797.44 eV, which could be achieved 10 mA cm−2 at an overpotential of 288 mV. Ni3S2@
attributed to the Co 2p3/2 and Co 2p1/2 peaks (Figure 4c). In NF achieved j = 100 mA cm−2 at an overpotential of 449 mV,
addition, two satellite peaks (indicated as “Sat.”) were also whereas CoSx/Ni3S2@NF achieved j = 100 and 200 mA cm−2
observed at 803.45 and 786.07 eV. Both Ni and Co XPS at overpotentials of 340 and 383 mV, respectively. CoSx@NF
spectra confirmed the presence of multiple oxidation states. achieved j = 100 and 200 mA cm−2 at overpotentials of 396
The peak at 168.2 eV in the S 2p spectrum (Figure 4d) could and 472 mV, respectively. The catalytic activity of CoSx/
be due to the presence of S atoms being at a higher oxidation Ni3S2@NF surpassed the activity of Pt/C@NF beyond an
state.11 Oxidation was unavoidable in the case of hydrothermal overpotential of 317 mV. The Tafel slope for CoSx/Ni3S2@NF
reaction; thus, the prepared electrocatalyst could have been derived from the Tafel plot (Figure 5b) was found to be of
dominated by sulfite (SO32−).50 This peak was also blue- 133.32 mV dec−1, which is less than that of Ni3S2@NF (slope
shifted in comparison to the peak observed in the S 2p spectra = 150.18 mV dec−1) and CoSx@NF (136.40 mV dec−1). All
of Ni3S2@NF (see Figure S4b). All the above observations these observations established the fact that CoSx/Ni3S2@NF
27716 DOI: 10.1021/acsami.8b04223
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Figure 6. (a) HER polarization curves for CoSx/Ni3S2@NF before and after 500 CV cycles at 100 mV s−1 scan rate and (b) chronoamperometric
curve for CoSx/Ni3S2@NF recorded at an overpotential of 300 mV for ∼10 h and 350 mV for another ∼10 h (no iR correction).

Figure 7. (a) OER polarization curves of CoSx/Ni3S2@NF, Ni3S2@NF, CoSx@NF, bare NF, and RuO2@NF in 1.0 M KOH (with iR correction),
(b) corresponding Tafel plots, (c) Nyquist plots of CoSx/Ni3S2@NF, Ni3S2@NF, CoSx@NF, and bare NF at an overpotential of 300 mV, and (d)
Δjν−1/2 vs ν1/2 plots of CoSx/Ni3S2@NF, Ni3S2@NF, CoSx@NF, and bare NF.

performed better as an electrocatalyst for HER than Ni3S2@ equivalent to an overpotential of 200 mV for HER, and the
NF and CoSx@NF. It is well-known that in alkaline medium, corresponding Nyquist plot is shown in Figure 5c. The
HER proceeds through water dissociation and adsorption of H presence of a capacitive semicircle in the Nyquist plots
(Volmer step) and then desorption of Hads either chemically confirmed that the electrocatalysis process is dynamically
(Tafel) or electrochemically (Heyrovsky).51 From the Tafel controlled and can be characterized by a single time constant.
slope, it is possible to predict the rate-determining step. In the This observation was in close agreement with the fact that the
present study, the Volmer step was predicted to be the rate- HER process is controlled by a charge-transfer step.52 The
determining step, that is charge-transfer resistance (RCT) of CoSx/Ni3S2@NF was
H 2O + e− → Hads + OH− found to be ∼29.2 Ω, whereas ∼98.59 and ∼53.81 Ω RCT
(8)
were recorded for Ni3S2@NF and CoSx@NF, respectively
The exchange current density (j0) values of the materials (Figure S7). It can be anticipated that because of nanointerface
were also obtained from the Tafel plot. The j0 values of CoSx/ formation, the charge transfer between Co and Ni was
Ni3S2@NF, CoSx@NF, and Ni3S2@NF were found to be facilitated via an S-bridge, which in turn facilitated the charge
0.287, 0.177, and 0.151 mA cm−2, respectively. The obtained transfer between the electrocatalyst and the electrolyte. This
value suggested that in an equilibrium condition, the intrinsic finding was in accordance with the inference obtained from the
charge-transfer efficiency of CoSx/Ni3S2@NF is better than j0 value calculation.
that of both CoSx@NF and Ni3S2@NF electrodes. For further The HER catalysis activity was studied for C0.05NS and
insights into the HER kinetics, EIS studies of the electro- C0.2NS as well and was compared with CoSx/Ni3S2@NF,
catalysts had been performed by applying a dc potential CoSx@NF, and Ni3S2@NF (see Figure S8 for details).
27717 DOI: 10.1021/acsami.8b04223
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The durability of CoSx/Ni3S2@NF as the HER electro- better than both Ni3S2@NF and CoSx@NF, as an OER
catalyst was tested by performing 500 CV cycles with a scan electrocatalyst. For a better understanding of the OER
rate of 100 mV s−1 between 0 and −0.35 V (vs RHE). After the catalysis, the Nyquist plots were obtained (Figure 7c) from
500th cycle, an LSV scan was performed, and the obtained the EIS study, which was performed by applying a bias
polarization curve was compared with the initial polarization equivalent to an overpotential of 300 mV. The RCT for OER in
curve (Figure 6a). A negligible change in current density was the case of CoSx/Ni3S2@NF, Ni3S2@NF, and CoSx@NF was
observed. To further confirm the durability, chronoamperom- found to be 19.3, 35.2, and 82 Ω, respectively (Figure S9).
etry was performed at an overpotential of 300 mV for ∼10 h Thus, on the basis of electrochemical performances, it can be
and then again at an overpotential of 350 mV for another ∼10 concluded that CoSx/Ni3S2@NF showed better OER catalyz-
h. Interestingly, it was found that the catalyst retained ∼92.8% ing activity than Ni3S2@NF and CoSx@NF. Furthermore, from
current density (no iR correction) even after ∼20 h long the Nyquist plot, “true” capacitance values were calculated for
performance (Figure 6b). Both studies confirmed the long- CoSx/Ni3S2@NF and Ni3S2@NF (see Table S5). The
term performance ability of the prepared material as the HER capacitance value for CoSx/Ni3S2@NF was found to be
electrocatalyst. ∼2.78 times to that of Ni3S2@NF. In the case of CoSx@NF,
3.3. Electrochemical Oxygen Evolution Activity. The the calculated capacitance value was too low compared to
catalytic activity toward OER was studied with three-electrode CoSx/Ni3S2@NF.
setup by performing an LSV scan for RuO2@NF, CoSx/ Quantification of active site strategy is very useful to
Ni3S2@NF, Ni3S2@NF, CoSx@NF, and bare NF in 1.0 M comprehend the factors responsible for improved catalytic
KOH solution. The polarization curves (Figure 7a) of both performance. For all Ni-based OER catalysts, it is believed that
CoSx/Ni3S2@NF and Ni3S2@NF exhibited an oxidation peak the Ni(III) centers formed after oxidation of Ni(II) are the
at ∼1.34 V (vs RHE), which is due to the oxidation of Ni(II) potential active sites.56,57 Therefore, the amount of charge (Q)
to form Ni(III).28,53 In order to avoid the influence of involved in the oxidation of Ni(II) can be estimated by
oxidation peak toward the current density (j), an overpotential integrating the oxidation peak in the oxidation wave and
(η) required to achieve a j value of 20 mA cm−2 was dividing by scan rate (ν)
considered. It was observed that for CoSx/Ni3S2@NF, an E2
1
overpotential of 280 mV was required to achieve the j value of
20 mA cm−2 (η20). The efficiency and viability of the prepared
Q=
ν
∫E
1
i(E) dE
(10)
catalyst toward OER were compared with the prior published
studies, and it was seen that its activity is comparable with or As one electron is involved in this oxidation process, the
even better than some of the recently reported electrocatalysts number of Ni(III) centers can be estimated from Q, which in
in the alkaline medium (as shown in Table S4). When the turn gives the number of active sites, if assumed that all Ni(III)
same test was performed with Ni3S2@NF and CoSx@NF, the centers are catalytically active. Therefore,
required overpotentials to achieve a current density of 20 mA Q
cm−2 were 347 and 353, respectively. This suggested that the Number of active sites =
1.60217662 × 10−19 coulombs
impregnation of CoSx is advantageous for OER catalysis too. (11)
For comparison, the catalytic activity of RuO2@NF was
investigated, which showed a superior activity till 387 mV The number of catalytically active sites for CoSx/Ni3S2@NF
overpotential, but beyond that potential, its performance was and Ni3S2@NF was found to be 1.993 × 1018 and 0.683 × 1018
inferior to CoSx/Ni3S2@NF. The overpotential required to atoms cm−2, respectively (Figure S10). The number of active
achieve a current density of 20 mA cm−2 for both RuO2@NF sites became ∼2.92 times greater after incorporation of CoSx
and CoSx/Ni3S2@NF was almost the same, but RuO2@NF and as a consequence showed a better OER catalysis. This
achieved a current density of 50 mA cm−2 at a lower inference showed close agreement with the previous findings
overpotential of 14 mV than that of CoSx/Ni3S2@NF. For obtained from the Nyquist plot. In the case of CoSx@NF, the
CoSx/Ni3S2@NF, the η100 and η200 values were 373 and 414 Ni(II) oxidation peak was absent as the Ni site was not an
mV, respectively, whereas, for Ni3S2@NF, the η100 value was OER catalysis active site. Thus, active site quantification as
448 mV. For CoSx@NF, the η100 and η200 values were 440 and discussed above could not be done in the case of CoSx@NF.
509 mV, respectively. Bare NF required an overpotential of To further confirm the number of active sites, another
448 mV to achieve j = 20 mA cm−2, indicating its poor activity measuring approach was also used. The ECSA and RF values
toward OER. RuO2@NF achieved current densities of 100 and were calculated from the Cdl. It is a common practice to plot Δj
200 mA cm−2 at overpotentials of 371 and 432 mV, against ν for obtaining the Cdl value. However, because of the
respectively. To have more understanding on the OER kinetics presence of Faradaic influence in current density, linear
in the case of the prepared electrocatalyst, a Tafel plot (Figure variation deviates to some extent.58 As the Faradaic and
7b) was obtained and examined. Lowest and highest Tafel capacitive currents vary linearly with ν1/2 and ν, respectively,
́ et al. proposed a procedure to deconvolute the Faradaic
values were recorded for RuO2@NF (92.7 mV dec−1) and bare Diaz
NF (166.48 mV dec−1), respectively. The calculated Tafel component.59,60 From the following equation, it can be
slope values for CoSx/Ni3S2@NF, Ni3S2@NF, and CoSx@NF understood that plotting Δjν−1/2 against ν1/2 could furnish
were 105.4, 113.4, and 133 mV dec−1, respectively. From the the absolute Cdl value
Tafel slope values, the predicted rate-determining step for
Δjν−1/2 = K Cν1/2 + KF (12)
OER was the first electron transfer step as indicated below:
M + OH− → MOH + e− (9) where KC and KF are double-layer charging component and
Faradaic component, respectively. For each catalyst, the CV
where the catalytically active site is abbreviated as M.54,55 A scans with different scan rates (ν) of 20, 50, 80, 100, 120, 150,
smaller Tafel slope value signified that CoSx/Ni3S2@NF acted and 180 mV s−1 were performed between the potential range
27718 DOI: 10.1021/acsami.8b04223
ACS Appl. Mater. Interfaces 2018, 10, 27712−27722
ACS Applied Materials & Interfaces Research Article

Figure 8. (a) OER polarization curves for CoSx/Ni3S2@NF before and after 500 CV cycles at a scan rate of 100 mV s−1 and (b)
chronoamperometric curve for CoSx/Ni3S2@NF recorded at an overpotential of 350 mV for ∼10 h and 370 mV for another ∼10 h (no iR
correction).

Figure 9. (a) Polarization curves of CoSx/Ni3S2@NF||CoSx/Ni3S2@NF, Ni3S2@NF||Ni3S2@NF, CoSx@NF||CoSx@NF, bare NF||bare NF, and
RuO2@NF||Pt/C@NF in 1.0 M KOH (without iR correction); (b) chronoamperometric curve for CoSx/Ni3S2@NF||CoSx/Ni3S2@NF recorded at
1.9 V potential (no iR correction); and (c) polarization curves of CoSx/Ni3S2@NF||CoSx/Ni3S2@NF in 1.0 M KOH solution before and after ∼30
h long operation.

of 1.02−1.17 V (vs RHE) (see Figure S11 for cyclic The durability of CoSx/Ni3S2@NF under the OER
voltammograms). In each case, the Δj values at the potential catalyzing condition was tested by performing 500 CV cycles
of 1.07 V for different ν had been calculated, and Δjν−1/2 was from 1.23 to 1.58 V at a scan rate of 100 mV s−1. Only a small
plotted against ν1/2 (Figure 7d). From the slope, the derived change in the current density and shifting of oxidation
Cdl value for CoSx/Ni3S2@NF was 8.68 mF cm−2, which was potential toward a lower value by ∼10 mV were observed
found to be ∼2.35 times higher than that of Ni3S2@NF (3.69 when the initial and final polarization curves were compared
mF cm−2). In the case of CoSx@NF, the Cdl value was found to and matched (Figure 8a). After performing the chronoampero-
be 6.12 mF cm−2. From the Cdl values, the ECSA and RF were metric test at an overpotential of 350 mV for ∼10 h and again
calculated for each material (Table S6). The results achieved at 370 mV for the next ∼10 h, the catalyst found to retain
from both the approaches indicated greater active sites in ∼90.8% current density (no iR correction, Figure 8b). The FE-
CoSx/Ni3S2@NF than in Ni3S2@NF and CoSx@NF, suggest- SEM images of CoSx/Ni3S2@NF were recorded after OER
ing its superior electrocatalytic activity toward OER. The catalysis operation (see Figure S13), and it was found that the
polarization curves of OER were recorded for C0.05NS and morphology of the material was retained with very minute
C0.2NS and compared with CoSx/Ni3S2@NF, CoSx@NF, and changes. The EDXS analysis confirmed the presence of Ni, Co,
Ni3S2@NF (see Figure S12 for details). and S in the CoSx/Ni3S2@NF sample after the OER study.
27719 DOI: 10.1021/acsami.8b04223
ACS Appl. Mater. Interfaces 2018, 10, 27712−27722
ACS Applied Materials & Interfaces Research Article

The above studies proved that CoSx/Ni3S2@NF could be Ni3S2@NF a promising earth-abundant noble-metal-free
operated as the OER electrocatalyst for a long period. bifunctional electrocatalyst for overall water splitting applica-
3.4. Overall Water Splitting Activity. As the prepared tion in the alkaline medium.
catalyst exhibited good electrocatalytic activity toward both
HER and OER, a two-electrode system was constructed using
CoSx/Ni3S2@NF as both anode and cathode to explore its
■ ASSOCIATED CONTENT
* Supporting Information
S
overall water splitting competency. The constructed two- The Supporting Information is available free of charge on the
electrode electrolyzer required a potential of 1.572 and 1.863 V ACS Publications website at DOI: 10.1021/acsami.8b04223.
to acquire current densities of 10 and 50 mA cm−2, respectively
Digital photographs of bare NF, Ni3S2@NF, and CoSx/
(Figure 9a). The obtained values suggested that the bifunc-
tional electrocatalyst CoSx/Ni3S2@NF showed comparable Ni3S2@NF; FE-SEM images of C0.05NS and C0.2NS;
water splitting potentiality with respect to the recently reported EDXS spectrum of CoSx/Ni3S2@NF obtained from HR-
electrocatalysts, as summarized in Table S7. For comparison, a TEM; high-resolution XPS profiles of Ni 2p and S 2p of
two-electrode system consisting of Pt/C@NF and RuO2@NF Ni3S2@NF; polarization curves and corresponding Tafel
was fabricated, which required 1.573 V to achieve a current plots for Pt/C@NF and Pt wire; polarization curves and
density of 10 mA cm−2. Remarkably, the reference electrolyzer corresponding Tafel plots for Pt/C@NF with and
exhibited water splitting activity almost comparable to that of without using a binder; comparison of recently reported
CoSx/Ni3S2@NF||CoSx/Ni3S2@NF until 1.789 V potential. HER catalytic activity of Pt/C in 1.0 M KOH solution;
When the similar study was carried out for Ni3S2@NF, CoSx@ comparison of recently reported HER, OER, and
NF, and bare NF, it was found that the potentials required to bifunctional electrocatalysts; Nyquist plots for bare
achieve a current density of 10 mA cm−2 were 1.798, 1.778, NF, Ni3S2@NF, CoSx@NF, and CoSx/Ni3S2@NF in
and 1.904 V, respectively. the case of HER and OER along with circuit modules
Long-term operational durability was investigated by used to fit the curves; HER and OER polarization curves
performing chronoamperometry at 1.9 V for ∼30 h using for C0.05NS and C0.2NS, cyclic voltammograms for
CoSx/Ni3S2@NF as both cathode and anode in 1.0 M KOH Ni3S2@NF and CoSx/Ni3S2@NF along with integrated
solution. As depicted in Figure 9b, the electrocatalyst retained oxidation peaks; cyclic voltammograms at different scan
∼86.60% of its current density after ∼30 h long operation. rates for bare NF, Ni3S2@NF, and CoSx/Ni3S2@NF;
Further, to confirm the stability, LSV was performed, and the
FE-SEM images of CoSx/Ni3S2@NF after OER catalysis
obtained curve was compared with the initially obtained
performance; and XPS survey spectra of CoSx/Ni3S2@
polarization curve (Figure 9c). The final polarization curve was
slightly changed with a visible oxidation peak located at ∼1.4 NF (PDF)
V. The oxidation peak might appear because of the oxidation
of Ni sites after the longtime operation. The final polarization
curve showed that the electrocatalyst required 144 mV more
■ AUTHOR INFORMATION
Corresponding Author
overpotential than it initially required to achieve a current *E-mail: [email protected]. Phone: +91-9647205077. Fax: 91-
density of 10 mA cm−2. These observations confirmed the 343-2548204.
long-term operational efficiency of the electrocatalyst for ORCID
overall water splitting. Tapas Kuila: 0000-0003-0976-3285
4. CONCLUSIONS Author Contributions
This manuscript was written through contributions from all
In summary, a one-pot hydrothermal synthetic procedure to authors. All authors have given approval to the final version of
fabricate a binder-free CoSx/Ni3S2@NF electrode was the manuscript.
presented. Herein, the Ni foam not only acted as the
Notes
conducting material but also acted as the nickel source. The
The authors declare no competing financial interest.

■
porous structure of CoSx/Ni3S2@NF helped in the better
distribution of active sites and adsorptions of H- and O-
ACKNOWLEDGMENTS
containing intermediates at the active sites. The prepared
electrocatalyst showed an excellent activity because of the (a) The authors are thankful to the Director of CSIR-CMERI. The
elimination of the binder on electrode fabrication, (b) better authors also acknowledge the Department of Science and
charge-transfer efficiency because of Co−S−Ni moiety Technology, New Delhi, India, for the financial support vide
project numberGAP215312.

■
formation, (c) increment in the number of active sites, and
(d) decrease in H- and O-containing species adsorption-free
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27722 DOI: 10.1021/acsami.8b04223

ACS Appl. Mater. Interfaces 2018, 10, 27712−27722