Yang 2017

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e9
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Porous CoS2 nanostructures based on ZIF-9

supported on reduced graphene oxide: Favourable
electrocatalysis for hydrogen evolution reaction
Yuanyuan Yang, Feng Li, Wenzhu Li, Wenbing Gao, He Wen, Jing Li,
Yiping Hu, Yutong Luo, Rong Li*
State Key Laboratory of Applied Organic Chemistry (SKLAOC), College of Chemistry and Chemical Engineering,
Lanzhou University, Lanzhou, 730000, PR China
article info abstract
Article history: The research and developments of porous, highly active non-noble metal cathode mate-
Received 8 October 2016 rials are the current hot spots. In our work, ZIF-9 (Zeolitic imidazolate framework-9) as a
Received in revised form cobalt source provide porous structure, we have sulfurized the ZIF-9 into CoS2 by a simple
18 January 2017 hydrothermal method. Ultimately, the porous CoS2/RGO cathode material was obtained.
Accepted 28 January 2017 Through a series of characterization analyses (powder X-ray diffraction, X-ray photoelec-
Available online xxx tron spectroscopy), it is confirmed that the CoS2/RGO composite was successfully formed.
Furthermore, electrochemical tests demonstrated that the pursued catalyst exhibited
Keywords: remarkable hydrogen evolution reaction (HER) activities with a favorable overpotential
Hydrogen evolution reaction (only 180 mV for 10 mA cm2 vs reversible hydrogen electrode), a low Tafel slopes
Porous CoS2 nanostructure (75 mV decade1) and high stability in acidic condition (more than 18 h).
Hydrothermal © 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Reduced graphene oxide
low-cost elements are still absent [6e8]. In order to proceed

Introduction electrochemical water splitting, impressed voltage defined as
overpotential (h) must be applied [9]. Therefore, reduction of
In recent decades, global warming and the energy crisis have overpotential by catalysts is critical to reduce the consumption
become increasingly prominent, therefore, there has been a of energy. Generally, Platinum (Pt) group metal elements have
growing need to replace fossil fuels. Hydrogen energy has been the lowest overpotential in HER, but its wide application in
considered as a suitable substitute for fossil fuels [1,2] since it is industrial area is actually limited because of valuableness and
clean and its burning does not produce greenhouse gasses [3,4]. exiguity [10,11]. Hence, interests in designing and investigating
Among numerous processes for preparing hydrogen, Electro- efficient non-precious-metal catalysts and the corresponding
lytic hydrogen production has unique advantages including application in hydrogen evolution reaction have been carrying
that the electrolysis system can act as an energy vector and on [12e14].
energy storage medium [5]. However, several doubts have been Among many materials, transition metal sulfides are
remained in this hype, mainly because: 1) generating hydrogen attracting extensive attention. Tremendous works have
by electrolysis of water system is still difficult, 2) steady and demonstrated that transition metal sulfides possess high ef-
efficient electrocatalysts composed of earth-abundant and ficiency to HER. Co-based sulfide which possesses more
* Corresponding author.
E-mail address: liyirong@lzu.edu.cn (R. Li).
http://dx.doi.org/10.1016/j.ijhydene.2017.01.186
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article in press as: Yang Y, et al., Porous CoS2 nanostructures based on ZIF-9 supported on reduced graphene oxide:
Favourable electrocatalysis for hydrogen evolution reaction, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/
j.ijhydene.2017.01.186
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e9
prominent advantages than layered transition metal disul- final catalysts. First of all, ZIF-9/RGO composite precursor was
fides electrocatalysts like MoS2 and WS2, have been thought to prepared by using a facile hydrothermal process by mixing
be promising substitute for commercial Pt/C towards HER [15]. cobalt ions, benzimidazole ligands and RGO. Then, the as-
However, their performances are still not satisfying. Recently, prepared ZIF-9/RGO was sulfurized by S powders to form
porous materials have received widespread attention because CoS2/RGO via a further hydrothermal method. In this process,
they are more conducive to the transfer of electrons and the morphology and structure of ZIF-9 was destroyed and
masses. Specifically, metal-organic frameworks (MOFs), ligand was placed by S2 2 ligand, thus central Co2þ ion was
2
which are constructed through coordination of metal ions and combined with S2 ligand to form CoS2. By comparing the
organic ligands, have been considered as promising pre- different reaction time, reaction temperature and carrier
cursors to construct porous structures, and widely applied in quantity, the optimal catalyst is CoS2/RGO (10 wt. %, 12 h,
gas storage/separation [16], catalysis [17], drug delivery [18], 200 C) (Supporting information, Fig. 4S). The synthesized
sensors [19]. However, MOFs are not electronically conductive, electrocatalyst exhibited superior HER activity in acidic me-
limiting their applications in water splitting. Several dium, which shows an overpotential of 180 mV at the
literature have reported solutions to this problem, for cathodic current density of 10 mA cm2. What's more, the
instance, the MOFs template was annealed under inert at- Tafel slope is 75 mV decade1 and the exchange current
mosphere contribute to form N-rich conductive carbon matrix density is 391 mA cm2. Meanwhile, the obtained objective
[20]. Moreover, the MOFs templates are directly converted to material shows good long-term stability.
metal oxides, metal sulfides, metal phosphides, metal sele-
nides by introducing other elements (O, S, P, Se, etc.) during
the annealing process [21,22]. Very recently, Huang and co- Experimental
workers have employed MOFs as the precursor template to
derive hollow structure pursued electrocatalysts and its Reagents
excellent HER activity has been confirmed. In addition, the
introduction of oxidized graphene could further improve the All reagents and starting materials used in this study were of
conductivity of MOFs. In this work, to develop MOF-based analytical grade without further purification, redox Graphene
porous HER electrocatalysts [23e25], Porous ZIF-9 as a cobalt was purchased from XF NANO INC Advanced Material
source and sacrificial template is used to synthesize porous Supplier, Cobalt nitrate hexahydrate (Co(NO3)2$6H2O) was
CoS2, at the same time, the introduction of graphene can purchased from TIANJIN GUANGFU TECHNOLOGY DEVELOP-
further enhance the conductivity of materials, and improve MENT Co. Ltd, sulfuric acid, sulphur powder, octylamine,
the dispersion of CoS2. The composite of CoS2/RGO was syn- ethanol were obtained from Sinopharm Chemical Reagent Co.
thesized by a facile hydrothermal method, which can properly Ltd. Benzimidazole was purchased from CHINA SHANGHAI
solve the problems of the traditional method, such as the REAGENTS FACTORY.
dispersion degree of active components and agglomeration. In
the present composite materials, as-synthesized catalyst have Synthesis of ZIF-9/RGO
relatively lower onset potential and overpotential, and the
CoS2/RGO (10 wt. %) shows the best HER performance. Cobalt nitrate hexahydrate (Co(NO3)2$6H2O (0.210 g))
In order to more intuitively and clearly describe the and benzimidazole (0.170 g) were dissolved with N, N-dime-
experiment procedure, and therefore essential to the flow- thylformamide (DMF) (72 mL) in a 100 mL round-bottom flask.
process diagram (Scheme 1). Scheme 1 is a schematic illus- Different quantity percentage of redox Graphene (1%, 5%, 10%,
tration showing the synthetic route from initial material to 20%, 30% on account of the total mass of starting solid
Scheme 1 e Illustration of the formation of CoS2/RGO nanocomposites.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e9 3
reactant) were added to the mixtures. After sonicating the Materials characterizations
solution, the vessel was sealed and heated up to 130 C with a
heating rate of 5 C min1 in an oven for 48 h followed by slow The morphologies of the samples were characterised by
cooling to room temperature at 0.4 C min1. Finally, the transmission electron microscope (Tecnai G2Tf20 operated at
purple-black crystals were obtained, then as-synthesized 300 KV). For TEM studies, the samples were acquired by
materials filtrated and washed with ample DMF and dried placing a drop of the ethanol suspension on a copper grid. The
under vacuum. crystalline structure of the synthesized nanophase was per-
formed by X-ray diffraction (XRD Rigaku D/max-2400 diffrac-
Preparation of CoS2/RGO tometer) in the range of 10e90 . Raman spectra were collected
using a inVia Renishaw confocal spectroscopy at an excitation
For preparing the CoS2/RGO hybrid, the 1.8 mmol S powders wavelength of 633 nm. BET surface area was performed by N2
and 27 mg MOF/RGO were added to the mixed solution of adsorption/desorption analysis method at 197.2 C on Tristar
ethanol (13 ml) and octylamine (14 ml). Then, sonication of P 3020 instrument. Chemical compositions and valence band
the mixture solution at room temperature for about 30 min spectra of samples were obtained by X-ray photoelectron
until a homogeneous solution was obtained. Afterward the spectroscopy (XPS PHI-5702 instruments). Electrochemical
reaction solution was placed to a 50 ml Teflon-lined auto- tests were carried out with a model CH Instrument 660E
clave, and put the autoclave into reaction kettle. The kettle electrochemical workstation (Shanghai Chenhua Equipment,
was heated in an oven at 200 C for 12 h. When the sulfuri- China).
zation reaction was completed, the obtained suspension was
centrifuged at 9000 rpm for 10 min, the obtained solute was
washed with ethanol several times and dried under vacuum Results and discussion
at 50 C.
Investigating the morphology and microstructure of the syn-
Preparation of catalyst electrode
thesized a series of precursors and pursued catalyst of CoS2/
RGO by TEM and HRTEM (Fig. 1). Fig. 1a exhibits the TEM image
Before electrochemical testing, firstly, glassy carbon electrode
of ZIF-9, it is clearly observed that the well-defined typical
was polished with Al2O3 powder, then it was rinsed with
structure of ZIF-9. Upon hydrothermal condition, the cobalt
deionized water and ethanol and allow to dry. The working
ions react with benzimidazole ligand to form ZIF-9, and gra-
electrodes were fabricated as follows: 4 mg Catalysts and 30 mL
phene is introduced into reaction system to obtain ZIF-9/RGO
(0.5 wt. %) Nafion solutions were dispersed in 1 mL of a solu-
composite in Fig. 1b. As we can see in Fig. 1b, the wrinkle
tion of deionized water and ethanol (3:1 in volume ratio). After
indicate the presence of graphene. The CoS2/RGO composite
sonicating 1 h, the solution became a homogeneous ink, and
catalysts were revealed by low-resolution electron micro-
5 mL the catalyst dispersion was pipetted and spread on the top
scope (TEM) (Fig. 1c). From Fig. 1c, it is obviously observed that
of a GCE. The catalyst-coated GCE was dried in air (catalyst
the active component of CoS2 successfully and homoge-
loading of 0.285 mg cm2). By means of Nernst equation:
neously grew up on the skin of graphene, in the process of
ERHE ¼ ESHE þ 0.0591 pH ¼ EAppl þ 4Ag/Agcl þ 0.0591 pH, all
sulfurized ZIF-9/RGO. Compared with Fig. 1b and c, we obvi-
the measured potentials were converted to the reversible
ously find that the size of ZIF-9 at average range 200 nm to
hydrogen electrode (RHE) scale, in which ESHE is the potential
even bigger change into CoS2 nanoparticles with small
versus standard hydrogen electrode (SHE) potential, EAppl is
average size of around 50 nm. Meanwhile, we measured 100
the applied potential vs. Ag/AgCl reference, and 4Ag/Agcl is the
particles from Fig. 1c, estimating particles to be about 50 nm,
electrode potential of the KCl-saturated Ag/AgCl reference
and we made the size distribution histogram which showed in
electrode (0.198 V vs. SHE).
the inset of Fig. 1c. Fig. 1d shows the partial enlarged drawing
of CoS2/RGO composite catalysts, for detecting the chemical
Electrochemical studies
composition, the energy dispersive X-ray (EDX) analysis has
been showed in inset of Fig. 1d. The EDX analysis of CoS2/RGO
The electrochemical experiments were carried out in a stan-
reveals the existence of Co, S elements, then the atomic pro-
dard three-electrode setup in 0.5 M H2SO4 solution (using
portions (Co and S) is close to 1:2, furtherly confirming the
catalyst-coated GCE as working electrode, a Pt wire as the
formation of CoS2 electro-catalysis active component. By
counter electrode and Ag/AgCl as the reference electrode). The
observation of Fig. 1d, CoS2 particles are bright and dark,
experiments were done by Linear Sweep voltammetry (LSV) at
which indicates the pore structure of CoS2. Fig. 1e is the
a scan rate of 5 mV s1. Before each experiment, bubbling N2 to
magnified TEM of CoS2/RGO, which shows the edge of an in-
degas in electrolyte for 15 min. The electrochemical imped-
dividual CoS2 crystallite in graphene, the alternately dark and
ance spectroscopy (EIS) measurements were conducted in the
bright fringes shows the high crystallinity of CoS2. The lattice
frequency range of 105 to 0.01 Hz with a voltage excitation
space measurement of 0.276 nm is well corresponding to (200)
amplitude of 5 mV. In this work, all the potentials mentioned
lattice plane of CoS2 [26].
were referred to Eq (1).
For confirming the as-synthesized ZIF-9/RGO and CoS2/
ERHE ¼ EAg=AgCl þ 0:059pH þ Eq Ag=AgCl RGO, powder X-ray diffraction (XRD) patterns are showed in
(1) Fig. 2a. The diffraction peaks of CoS2/RGO are well
Eq Ag=AgCl ¼ 0:209V
matched with the standard diffraction pattern of CoS2 (JCPDS
Fig. 1 e TEM image of (a) ZIF-9 (b) ZIF-9/RGO (c) CoS2/RGO and HRTEM of CoS2/RGO are shown in image of (d), (e) and (f)
HRTEM of CoS2.
No. 41-1471). The peak position of CoS2 at 2q ¼ 32.3 , 36.2 , of the graphene at 2q ¼ 25 , which is contributed to (002)
39.8 , 46.3 and 56.4 , which are corresponded to (200), (210), planes [28]. However, in the XRD patterns of CoS2/RGO, the
(211), (220) and (311) faces [27], respectively. Both ZIF-9/RGO characteristic peak of the graphene has partially weaken,
and CoS2/RGO composite catalysts have the diffraction peak because the graphene has been restacked and aggregated
Fig. 2 e (a) XRD patterns of CoS2/RGO and ZIF-9/RGO, patterns of CoS2/RGO (JCPDS No.41-1471) standard is shown at the
bottom. (b) Raman spectra of RGO, ZIF-9/RGO and CoS2/RGO.
during the sulfurized ZIF-9/RGO process [29]. By means of XRD 778.3 eV and 793.3 eV in accordance with Co 2p3/2 and Co 2p1/2
pattern, we could observe that the characteristic peaks of ZIF- arised from cobalt sulfides [33,34]. Meanwhile, two apparent
9/RGO have hardly detected in diffraction pattern of CoS2/ peaks at 780.7 eV and 797.0 eV are related to Co 2p3/2 and Co
RGO, it is further confirmed that S2 2 ions combined with 2p1/2 from Co-O, which may result from the catalysts exposed
central Co2þ ions of ZIF-9 to form CoS2. Therefore, framework in the air. In addition, the rest of two peaks locating at 802.3 eV
of ZIF-9 has decomposed in the facile hydrothermal process. and 784.3 eV can be known as the shakeup satellites of Co2þ
To deeply research the composite catalysts of graphitic (denoted as “sat”) [35,36]. The S 2p peak shows in Fig. 3d, the
substrate, it is necessary to investigate the Raman spectra [30]. peaks at 161.3 and 162.6 are attributable to S 2p3/2 and S 2p1/2,
When graphitic products subjected to incident light excita- which arise from S2 adsorbed on the surface [37]. Near by the
tion, receiving and investigating different scattered spectrum, S2 peaks, there are two peaks (at 162.3 and 163.5 eV) agreed
we obtained the inset Fig. 2b. As can be seen, the samples also well with the bridging disulfides S2 2 ligands [38]. In addition,
have two special peaks, respectively locating around 1349 and two peaks higher than that of S 2p correspond to sulfide oxide
1586 cm1, which are well-corresponding to the D and G bands due to the sulphides are easy to infect by air [39]. All above
of characteristic peaks of graphene [31]. As we known, the these data demonstrate that the formation of CoS2. Besides, by
generation of D and G bands due to sp3-hybridization defect XPS analysis, we could observe a so weak nitrogen peak,
sites and sp2-bonded pairs. In general, the relative intensity which is probably originated from residual octylamine. In the
ratio of ID/IG can evaluate the defect of graphene, the value of sulfuration precursor process, octylamine is introduced as a
the CoS2/RGO is 1.18, which is higher than the value of RGO dispersant, which may be strongly adsorbed on the graphene
(0.87) and ZIF-9/RGO (1.05), indicating that during the sulfu- surface. Then, washing the catalysts many times, the content
ration ZIF-9/RGO procession the delocalized p Conjugation is of residual nitrogen has been very little. Meanwhile, by
partially destroyed. deconvoluting the N 1s spectra, the peaks are corresponding
The full XPS elemental survey is presented in Fig. 3a. The to NHþ 3 and NH2 [40], as can be seen in Fig. 6S.
detected elements are Co, S, C, and O as expected for CoS2/ By means of furtherly understand the formation process of
RGO. As can be seen in Fig. 3b, based on the C 1s XPS spectra, active component CoS2 and reaction mechanism, to the best
the peaks at 284.6, 285.7, 287.2 and 288.7 are corresponding to of our knowledge, a possible mechanism of formation of CoS2
the oxygen and carbon atoms in the forms CeC, CeO, C]O, by the ZIF-9 conversion was proven [41,42]. Firstly, sulfur
and COOH [32]. The Co 2p spectra is imaged in Fig. 3c by the powder is reduced by ethanol solvent (EtOH may act as
high-resolution XPS of the sample, deconvoluting the spectra reducing agent at high temperatures [43,44]). Then, remainder
can into six peaks, including the strong binding energies at S can be reduced to S2 to form S2 2 ligand. Eventually, S22
Fig. 3 e (a) Typical XPS survey spectrum, deconvoluted (b) C 1s spectra, (c) Co 2p spectra, (d) S 2p spectrum.
Fig. 4 e (a) Polarization curves collected on different catalysts (b) Polarization curves for CoS2/RGO based on different carrier
(RGO) amounts.
ligand react with Co2þ ions of the Co-MOF to form CoS2 The Tafel slope is a crucial indicator of HER catalyst per-
[25,45e48]. formance, the Tafel slope is decided to the rate-limiting step.
The HER performance of all samples were measured in For the most part, when the catalysts produce a required
0.5 M H2SO4 acidic solution at indoor temperature. The po- current, the catalyst with a lower Tafel slope needs a lower
larization curve recorded by the ZIF-9, ZIF-9/RGO, CoS2/RGO overpotential [49]. The Tafel plots were root in polarization
and commercial Pt/C showed in Fig. 4a at a scan rate of curve of Fig. 4a are revealed in Fig. 5a, where their linear
5 mV s1. It can be observed that CoS2/RGO with an over- portions were substitute into Tafel equation to receive Tafel
potential of 180 mV at 10 mA cm2 is smaller than those of ZIF- slopes. The smallest Tafel slope value of CoS2/RGO is
9, ZIF-9/RGO. From Fig .4a, as we known, ZIF-9 has a poor HER 75 mV decade1, this value is challenging near to the Pt/C
activity, so as-synthesized CoS2 by sulfured ZIF-9 can resolve, electrode. Simultaneity, the Tafel slope of CoS2/RGO is much
but CoS2 has a poor electrical conductivity, then redox gra- smaller than the slope observed for the ZIF-9/RGO
phene can overall overcome. Therefore, we explored the effect (117 mV decade1) and the ZIF-9 (157 mV decade1). In addi-
of redox graphene as carrier of target catalyst. The result is tion, for furtherly examining essential HER activity, the ex-
showed in Fig. 4b. The weights of ZIF-9 and the S powder are change current density jo is valuable used to measure [50]. The
kept constant, the weight content of redox graphene is iden- objective catalysts of CoS2/RGO (10 wt. %) exhibit the highest
tified as 1 wt. %, 3 wt. %, 5 wt. %, 10 wt. %, 15 wt. %, 20 wt. %, exchange current density at 391 mA cm2, compared to ZIF-9
30 wt. %, respectively. By this comparison in sharp contrast we (190 mA cm2) and ZIF-9/RGO (273 mA cm2), which is calcu-
can illustrate that the activity of CoS2/RGO (10 wt. %) is best lated by the suitable j-E data to the Tafel equation. By a site-to-
because of the most positive overpotential. Moreover, the site comparison, of each site were also measured according to
various RGO weight percentage shows a certain extent regu- Jaramillo's method, as we can see in Table 1, the CoS2/RGO
larity of catalyst activity, the catalyst activity of CoS2/RGO (10 wt. %) exhibits highest TOF value of 0.8 s1 [51]. Obviously,
firstly increased and reached the maximum value when the the CoS2/RGO (10 wt. %) shows low overpotential and over-
RGO weight percentage is 10 wt. %, afterward there was a potential, high exchange current density, small Tafel slope,
significantly reduced, which could result in that excess RGO high TOF value, indicating its favorable intrinsic HER
would reduce the magnitude of active site and RGO would performance.
aggregate. So the result proves appropriate amount of RGO To better investigate the enhancement of HER activity for
can be beneficial to significantly improving electro-catalysis CoS2/RGO. For estimating the relative differences in electro-
activity. chemically active surface area (ESA), we use the cyclic
Fig. 5 e (a) Tafel plots of different catalysts (b) the Cdl and relative electrochemically active surface area.
In addition, catalysts stability is another extremely essen-

Table 1 e Overpotential (the current density of
tial parameter by which to evaluate practical HER applica-
10 mA cm¡2), Tafel slopes, exchange current densities jo
and turnover frequencies (TOFs) for various catalysts. tions. To test the stability of CoS2/RGO hybrid catalyst in acidic
environment, we conducted long-term cycling test for 1000
Catalyst Overpotential Tafel jo TOF
cycles. As observed in Fig. 6a, the polarization curve of before
(mV) slope b (mA cm2) (s1)
(mV dec1) and after 1000 cycles shows negligible loss. Furtherly probing
the durability of the catalyst, continuously operating elec-
ZIF-9 420 158 190 0.4
ZIF-9/ 330 117 273 0.55
trolysis at a constant overpotential (50 mV), the insert of
RGO Fig. 6b shows the CoS2/RGO hybrid catalysts maintained well-
CoS2/RGO 180 75 391 0.8 deserved activity for about 18 h [52].
Additionally, the electrochemical impedance spectros-
copy was also performed to investigate the HER kinetics at
voltammogram (CV) method. Measured capacitive current for the electrode/electrolyte interface [53]. The EIS data was
the all catalysts as a function of scan rate, each samples were obtained from 0.5 M H2SO4. As well known that the linear
extracted the double layer capacitance (Cdl), the Dj ¼ jajc at a parts at low frequencies resulting from hydrogen adsorption,
given potential (0.15 V vs RHE) was plotted against the CV scan then the semicircle at high frequency is corresponding to the
rates (Fig. 6b). For reason of the capacitive current should be charge transfer process [54]. As can be seen in Fig. 7a, the
directly proportional to the surface area. Afterward, intro- Nyquist plots of ZIF-9, ZIF-9/RGO and CoS2/RGO were fitting
ducing graphene into ZIF-9, the dispersity and electro- into an equivalent electrical circuit, as revealed obviously
conductivity have been a significant improvement, thus ZIF-9/ decreased charge transfer resistance (Rct), it is indicated that
RGO catalyst has a larger value of double layer capacitance. the higher conductivity of ZIF-9/RGO due to the presence of
Then sulfurizing the ZIF-9 after, the morphology and structure graphene, as well as CoS2/RGO has the smallest Rct value
have changed a lot, there has an obviously decreased in the compared to ZIF-9 and ZIF-9/RGO at the same potential. For
surface area, then the double layer capacitance of as- CoS2/RGO (10 wt. %) catalyst, the two-time constant model
synthesized materials has reduced, but the target materials observed from Fig. 7b corresponding to depressed semicircle
still have excellent HER activity. in Fig. 7a.
Fig. 6 e (a) Durability measure of the functionalized CoS2/RGO electrode. (b) Time-dependent current density.
Fig. 7 e (a) Nyquist plots of ZIF-9, ZIF-9/RGO and CoS2/RGO (10 wt. %) at same potential (40 mV) (b) bode plots of CoS2/RGO
(10 wt. %) at potential of 40 mV.
[6] Wan L, Zhang JF, Chen YQ, Zhong C, Hu WB, Deng YD. Nickel
Conclusions phosphide nanosphere: a high-performance and cost-
effective catalyst for hydrogen evolution reaction. Int J
In summary, the porous nanostructures of CoS2/RGO com- Hydrogen Energy 2016;47:20515e22.
posites nanocatalysts were successfully fabricated only via [7] Zhang AH, Yu SJ, Jiang YM, Jia LP, Xia XH, Ye WC, et al. A
novel Pt@Te-reduced graphene oxide/polyimide composite
sulfuring ZIF-9/RGO in a facile hydrothermal process.
catalyst for hydrogen evolution. Int J Hydrogen Energy
Meanwhile, the introduced RGO with 2D conductive network
2015;40:16238e47.
is used to a special substrate, which could increase the [8] Mitov M, Chorbadzhiyska E, Rashkov R, Hubenova Y. Novel
electron transfer rate. The ZIF-9 presents very poor HER ac- nanostructured electrocatalysts for hydrogen evolution
tivity, the benzimidazole ligands of ZIF-9 were substituted by reaction in neutral and weak acidic solutions. Int J Hydrogen
S ions after adding sulfur sources (S powder) in the appro- Energy 2012;37:16522e6.
priate mention the value of 200 C and 1 atm hydrothermal [9] Abbaspour A, Sarvestani FN, Mirahmadi E. Electrocatalytic
behavior of carbon paste electrode modified with metal
temperature and pressure, in consequence, the formation of
phthalocyanines nanoparticles toward the hydrogen
CoS2 had excellent HER activity. This facile updating process evolution. Electrochim Acta 2012;76:404e9.
is possible to realize under suitable conditions e.g. mention [10] Wu ZZ, Fang BZ, Bonakdarpour A, Sun A, Wilkinson DP,
the conditions, and it is an effective way to optimize the Wang DZ. WS2 nanosheets as a highly efficient
electrocatalysts. Finally, the enhanced electrochemical be- electrocatalyst for hydrogen evolution reaction. Appl Catal B
haviours of CoS2/RGO catalysts including large cathode cur- 2012;125:59e66.
rents and a small Tafel slope, which is determined by its [11] Jiao LX, Li F, Li XZ, Ren R, Li J, Zhou XC, et al. Ultrathin PdTe
nanowires anchoring reduced graphene oxide cathodes for
highly electrical conductivity, largely active surface area and
efficient hydrogen evolution reaction. Nanoscale
long-term stability in acid condition. This facile method of 2015;7:18441e5.
using ZIF-9 as precursor template to prepare the CoS2/RGO [12] Tian JQ, Liu Q, Asiri AM, Sun XP. Self-supported nanoporous
nanohybrid material is an effective way to synthesize noble cobalt phosphide nanowire arrays: an efficient 3D hydrogen-
metal catalysts in HER. evolving cathode over the wide range of pH 0e14. J Am Chem
Soc 2014;136:7587e90.
[13] Wang MY, Wang Z, Yu XT, Guo ZC. Facile one-step
electrodeposition preparation of porous NiMo film as
Acknowledgements electrocatalyst for hydrogen evolution reaction. Int J
Hydrogen Energy 2016;40:2173e81.
This research was supported by the National Science- [14] Ghasemi S, Hosseini SR, Nabipour S, Asen P. Palladium
technology Support Plan Projects (no. 2014BAK16B01), the nanoparticles supported on graphene as an efficient
Key Laboratory of Catalytic Engineering of Gansu Province and electrocatalyst for hydrogen evolution reaction. Int J
Resources Utilization, Gansu Province for financial support. Hydrogen Energy 2015;40:16184e91.
[15] Ouyang CB, Wang X, Wang SY. Phosphorus-doped CoS2
This work was supported by the National Natural Science
nanosheet arrays as ultra-efficient electrocatalysts for
Foundation of China (No. 51602138). hydrogen evolution reaction. Chem Commun 2013;51:14160e3.
[16] Jhung SH, Khan NA, Hasan Z. Analogous porous
metaleorganic frameworks: synthesis, stability and
Appendix A. Supplementary data application in adsorption. CrystEngComm 2012;14:7099e109.
[17] Dong ZP, Le XD, Liu YS, Dong CX, Ma JT. Metal organic
framework derived magnetic porous carbon composite
Supplementary data related to this article can be found at
supported gold and palladium nanoparticles as highly
http://dx.doi.org/10.1016/j.ijhydene.2017.01.186.
efficient and recyclable catalysts for reduction of 4-
nitrophenol and hydrodechlorination of 4-chlorophenol. J
references Mater Chem A 2014;2:18775e85.
[18] Cui Y, Li B, He HJ, Zhou W, Chen BL, Qian GD. Metal-organic
frameworks as platforms for functional materials. Acc Chem
Res 2016;49:483e93.
[1] Turner JA. A realizable renewable energy future. Science
[19] Surya SG, Nagarkar SS, Ghosh SK, Sonar P, Rao VR. OFET
1999;285:687e9.
based explosive sensors using diketopyrrolopyrrole and
[2] Liu Y, Li J, Li F, Li WZ, Yang HD, Zhang XY, et al. A facile
metal organic framework composite active channel material.
preparation of CoFe2O4 nanoparticles on polyaniline-
Sens Actuators B 2016;223:114e22.
functionalised carbon nanotubes as enhanced catalysts for
[20] Li XZ, Fang YY, Li F, Lin XQ, Tian M, An XC, et al. MOF derived
the oxygen evolution reaction. J Mater Chem A
Co3O4 nanoparticles embedded in N-doped mesoporous
2016;4:4472e8.
carbon layer/MWCNTs hybrids: extraordinary bi-functional
[3] Xu SJ, Li D, Wu PY. One-pot, facile, and versatile synthesis of
electrocatalysts for OER and ORR. J Mater Chem A
monolayer MoS2/WS2 quantum dots as bioimaging probes
2015;3:17392e402.
and efficient electrocatalysts for hydrogen evolution
[21] Huang ZF, Song JJ, Li K, Tahir M, Wang YT, Pan L, et al.
reaction. Adv Funct Mater 2015;25:1127e36.
Hollow cobalt-based bimetallic sulfide polyhedra for efficient
[4] Liang YH, Liu Q, Luo YL, Sun XP, He YQ, Asiri AM.
all-pH-value electrochemical and photocatalytic hydrogen
Zn0.76Co0.24S/CoS2 nanowires array for efficient
evolution. J Am Chem Soc 2016;138:1359e65.
electrochemical splitting of water. Electrochim Acta
[22] Hao JH, Yang WS, Zhang Z, Tang JL. Metaleorganic
2016;190:360e4.
frameworks derived CoxFe1xP nanocubes for
[5] Xiong K, Li L, Deng ZH, Xia MR, Chen SG, Tan SY, et al. RuO2
electrochemical hydrogen evolution. Nanoscale
loaded into porous Ni as a synergistic catalyst for hydrogen
2015;7:11055e62.
production. RSC Adv 2014;4:20521.
[23] Huang YY, Xiao YL, Huang HL, Liu ZP, Liu DH, Yang QY, et al. [39] Gao MR, Cao X, Gao Q, Xu YF, Zheng YR, Jiang J, et al.
Ionic liquid functionalized multi-walled carbon nanotubes/ Nitrogen-doped graphene supported CoSe2 nanobelt
zeolitic imidazolate framework hybrid membranes for composite catalyst for efficient water oxidation. ACS Nano
efficient H2/CO2 separation. Chem Commun 2014;8:3970e8.
2015;51:17281e4. [40] Alexander S, Morrow L, Lord AM, Dunnill CW, Barron AR. pH-
[24] Faber MS, Dziedzic R, Lukowski MA, Kaiser NS, Ding Q, Jin S. responsive octylamine coupling modification of carboxylated
High-performance electrocatalysis using metallic cobalt aluminium oxide surfaces. J Mater Chem A 2015;3:10052e9.
pyrite (CoS) micro- and nanostructures. J Am Chem Soc [41] Mahmood N, Zhang CZ, Jiang J, Liu F, Hou YL. Multifunctional
2014;136:10053e61. Co3S4/graphene composites for lithium ion batteries and
[25] Wang QH, Jiao LF, Han Y, Du HM, Peng WX, Huan QN, et al. oxygen reduction reaction. Chem Eur J 2012;19:5183e90.
CoS2 hollow spheres: fabrication and their application in [42] Mosselmans JFW, Pattrick RAD, Laan GVD, Charnock JM,
lithium-ion batteries. J Phys Chem C 2011;115:8300e4. Vaughan DJ, Henderson CMB, et al. X-ray absorption near-
[26] Cho K, Han SH, Suh MP. Copper-organic framework edge spectra of transition metal disulfides FeS2 (pyrite and
fabricated with CuS nanoparticles: synthesis, electrical marcasite), CoS2, NiS2 and CuS2, and their isomorphs FeAsS
conductivity, and electrocatalytic activities for oxygen and CoAsS. Phys Chem Miner 1995;22:311e7.
reduction reaction. Angew Chem Int Ed 2016;128:1e7. [43] Gao JH, Liang GL, Zhang B, Kuang Y, Zhang XX, Xu B.
[27] Zhang C, An B, Yang L, Wu BB, Shi W, Wang YC, et al. Sulfur- FePt@CoS2 yolkshell nanocrystals as a potent agent to kill
doping achieves efficient oxygen reduction in pyrolyzed HeLa cells. J Am Chem Soc 2007;129:1428e33.
zeolitic imidazolate frameworks. J Mater Chem A [44] Luo FL, Li J, Yuan HY, Xiao D. Rapid synthesis of three-
2016;4:4457e63. dimensional flower-like cobalt sulfide hierarchitectures by
[28] Bonet F, Delmas V, Grugeon S, Urbina RH, Silvert PY, microwave assisted heating method for high-performance
Elhsissen KT. Synthesis of monodisperse Au, Pt, Pd, Ru and Ir supercapacitors. Electrochim Acta 2014;123:183e9.
nanoparticles in ethylene glycol. Nanostruct Mater [45] Xie JF, Zhang JJ, Li S, Grote FB, Zhang XD, Zhang H, et al.
1999;11:1277e84. Controllable disorder engineering in oxygen-incorporated
[29] Xiong YJ, McLellan JM, Chen JY, Yin YD, Li ZY, Xia YN. MoS2 ultrathin nanosheets for efficient hydrogen evolution. J
Kinetically controlled synthesis of triangular and hexagonal Am Chem Soc 2013;135:17881e8.
nanoplates of palladium and their SPR/SERS properties. J Am [46] Liu Q, Zhang JY. A general and controllable synthesis of
Chem Soc 2005;127:17118e27. ComSn (Co9S8, Co3S4, and Co1xS) hierarchical microspheres
[30] Chakraborty I, Malik PK, Moulik SP. Preparation and with homogeneous phases. CrystEngComm 2013;15:5087e92.
characterisation of CoS2 nanomaterial in aqueous cationic [47] Ghahremaninezhad A, Dixon DG, Asselin E. Electrochemical
surfactant medium of cetyltrimethylammonium bromide and XPS analysis of chalcopyrite (CuFeS2) dissolution in
(CTAB). J Nanopart Res 2006;8:889e97. sulfuric acid solution. Electrochim Acta 2013;87:97e112.
[31] Zheng YH, Cheng Y, Wang YS. Metastable g-MnS hierarchical [48] Lin JY, Chou SW. Cathodic deposition of interlaced
architectures: synthesis, characterization, and growth nanosheet-like cobalt sulfide films for high-performance
mechanism. J Phys Chem B 2006;110:8284e8. supercapacitors. RSC Adv 2013;3:2043e8.
[32] Li F, Kong T, Bi WT, Li DC, Li Z, Huang XT. Synthesis and [49] Li F, Zhang L, Li J, Lin XQ, Li XZ, Fang YY, et al. Synthesis of
optical properties of CuS nanoplate-based architectures by a CueMoS2/rGO hybrid as non-noble metal electrocatalysts for
solvothermal method. Appl Surf Sci 2009;255:6285e9. the hydrogen evolution reaction. J Power Sources
[33] Liu J, Xue DF. Solvothermal synthesis of CuS semiconductor 2015;292:15e22.
hollow spheres based on a bubble template route. J Cryst [50] Chen WF, Sasaki K, Ma C, Frenkel AI, Marinkovic N,
Growth 2009;311:500e3. Muckerman JT, et al. Hydrogen-evolution catalysts based on
[34] Duan XL, Gao ZY, Chang JL, Wu DP, Ma PF, He JJ, et al. non-noble metal nickelemolybdenum nitride nanosheets.
CoS2egraphene composite as efficient catalytic counter Angew Chem Int Ed 2012;51:6131e5.
electrode for dye-sensitized solar cell. Electrochim Acta [51] Merki D, Fierro S, Vrubel H, Hu XL. Amorphous molybdenum
2013;114:173e9. sulfide films as catalysts for electrochemical hydrogen
[35] Peng SJ, Li LL, Han XP, Sun WP, Srinivasan M, Mhaisalkar SG, production in water. Chem Sci 2011;2:1262e7.
et al. Cobalt sulfide nanosheet/graphene/carbon nanotube [52] Lin XQ, Li XZ, Li F, Fang YY, Tian M, An XC, et al. Precious-
nanocomposites as flexible electrodes for hydrogen Metal-free Co-Fe-Ox coupled nitrogen-enriched porous
evolution. Angew Chem Int Ed 2014;126:12802e7. carbon nanosheets derived from schiff-base porous
[36] Li F, Li J, Cao Z, Lin XQ, Li XZ, Fang YY, et al. MoS2 quantum polymers as superior electrocatalysts for oxygen evolution
dot decorated RGO: a designed electrocatalyst with high reaction. J Mater Chem A 2013;4:6505e12.
active site density for the hydrogen evolution reaction. J [53] Yagati AK, Lee T, Min JH, Choi JW. Amperometric sensor for
Mater Chem A 2015;3:21772e8. hydrogen peroxide based on direct electron transfer of
[37] Gao ZY, Liu N, Wu DP, Tao WG, Xu F, Jiang K. GrapheneeCdS spinach ferredoxin on Au electrode. Bioelectrochem
composite, synthesis and enhanced photocatalytic activity. 2010;80:169e74.
Appl Surf Sci 2012;258:2473e8. [54] Ziyatdinova G, Galandova J, Labuda J. Impedimetric
[38] Xia XH, Zheng ZX, Zhang Y, Zhao XJ, Wang CM. Synthesis of nanostructured disposable DNA-based biosensors for the
MoS2-carbon composites with different morphologies and detection of deep DNA damage and effect of antioxidants. Int
their application in hydrogen evolution reaction. Int J J Electrochem Sci 2008;3:223e35.
Hydrogen Energy 2014;39:9638e50.

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i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e9

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/he

Porous CoS2 nanostructures based on ZIF-9

article info abstract

low-cost elements are still absent [6e8]. In order to proceed

Scheme 1 e Illustration of the formation of CoS2/RGO nanocomposites.

In addition, catalysts stability is another extremely essen-

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