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Accepted Manuscript: Infrared Physics & Technology
Accepted Manuscript: Infrared Physics & Technology
Accepted Manuscript: Infrared Physics & Technology
PII: S1350-4495(17)30203-7
DOI: https://doi.org/10.1016/j.infrared.2018.01.014
Reference: INFPHY 2472
Please cite this article as: M.B. Muradov, O.O. Balayeva, A.A. Azizov, A.M. Maharramov, L.R. Qahramanli, G.M.
Eyvazova, Z.A. Aghamaliyev, Synthesis and characterization of cobalt sulfide nanoparticles by sonochemical
method, Infrared Physics & Technology (2018), doi: https://doi.org/10.1016/j.infrared.2018.01.014
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Synthesis and characterization of cobalt sulfide nanoparticles by sonochemical method
ABSTRACT
CoxSy/3-MPA nanocomposites were carried out in the presence of ultrasonic irradiation by the
liquid phase synthesis of the sonochemical method. For the synthesis, cobalt acetate tetrahydrate
[Co(CH3COO)2·4H2O] and sodium sulfide (Na2 S·9H2O) were used as a cobalt and sulfur
precursor, respectively. Polyvinyl alcohol (PVA), ethylene glycol (EG) and 3-mercaptopropionic
acid (3-MPA) were used as a capping agent and surfactant. The structural, optical properties and
scanning electron microscopy (SEM). The optical band gap of Co9S8/PVA is 1.81 eV and for
CoxSy/EG is 2.42 eV where the direct band gap of bulk cobalt sulfide is (0,78-0,9 eV). The wide
band gap indicates that synthesised nanocomposites can be used in the fabrication of optical and
photonic devices. The growth mechanisms of the Co 9S8, CoS2 and Co3S4 nanoparticles were
discussed by the reactions. The effects of sonication time and annealing temperature on the
1. INTRODUCTION
Nanomaterials have received significant attention due to their wide range of applications in
various fields like catalysis, solar cells, batteries, photocatalysis and sensors [1]. The enormous
local temperature, pressure and the extraordinary heating/cooling rates generated by cavitational
collapse provide an unusual mechanism for generating high energy chemistry [2]. This method
has become an important tool in the synthesis chemistry to generate novel nano-sized materials
under ambient conditions in recent years [3, 4]. A major advantage of this methodology is that
the shape and size of the nanoparticles can be adjusted by varying the operating parameters
which include ultrasonic power, current density and times. Together with these, it is also possible
to adjust the pH, temperature and composition of the electrolyte in the sonoelectrochemistry cell
[5].
Fe3O4 powder with particle sizes 50 nm was used as catalyst precursor for the growth of
MWCNTs by chemical vapor deposition technique [6]. Prior to chemical vapor deposition
experiments, Fe3O4 powder was blended in ethanol by ultrasonic agitation [6, 7]. Authors noted
that undiluted CH4 was used as both reducing agent and C source because it is relatively cheap,
Cobalt sulfide compounds with different stoichiometric compositions, such as CoS 2, CoS,
Co9S8 and Co1-xS, have attracted great attention due to their physical, chemical, electronic and
optical properties and their wide potential applications in catalysts [8-10], electrochemical
supercapacitors [11-13] and Li-ion batteries [14-17]. Recently, synthesized cobalt sulfides with
different morphologies such as nanotubes [18, 19], nanowires [20], hollow sphere [21, 22] have
been successfully prepared by the different method. Hamid Emadi et al. were synthesized
concentrations of TGA and Co(CH3COO)2·4H2O using non-toxic precursor and solvent. Their
study has shown that the reaction times, temperature and concentrations of the reactants have a
great effect on the morphology and size distribution of the samples [23]. However, there are
quite a few reports on the synthesis of cobalt sulfides by the sonochemical method.
The possible existence of stable or metastable polysulfides of iron group metals was
particularly interesting, because of the familiarity and stability of FeS 2, CoS2, and NiS2.
Amorphous polysulfides of iron, cobalt, and nickel were prepared by precipitation from aqueous
solution followed by heating to remove water and pyrolyze the initially formed unstable product
to a metastable species [24]. The resulting compounds, Co 2S7, Co2S9, Ni2S7, and Fe3S8 were
evaluated as cathode materials in organic electrolyte lithium batteries. The cobalt compounds, in
particular, delivered very high capacities of 1-1.2 A-h/g at voltages around 1.8V. The resulting
In this work, cobalt sulfides/PVA, cobalt sulfides/EG, and cobalt sulfides/3-MPA powder
using PVA and mixed crystal phase Co xSy nanoparticles with CoS2 and Co3S4 content was
obtained using EG and 3-MPA as a surfactant substance and a capping agent. The effects of
sonication time and annealing temperature on the properties have been studied in detail. The
synthesized particles size decreased by increasing sonication time and annealing temperature.
2. EXPERIMENTAL
Cobalt sulfide nanoparticles were synthesized in the presence of ultrasonic irradiation by the
Na2S·9H2O, polyvinyl alcohol (PVA), ethylene glycol (EG) and 3-mercaptopropionic acid (3-
MPA)] were of analytical grade. For the synthesis, cobalt acetate tetrahydrate and sodium sulfide
were used as the precursor materials. Distilled water was used for all the experiments. Bath type
ultrasonicator (VCX500) was used for the synthesis of cobalt sulfide nanoparticles.
added to the 40 ml 5% PVA solution and ultrasonically stirred for 2h at room temperature. By
circulating cold water the temperature of the ultrasonic bath was maintained constant. Formed
black precipitate was washed with distilled water and air dried. The experiment was conducted at
35 kHz frequency.
stirred. Then this two solutions were mixed and ultrasonically stirred for different sonication
times (1h, 2h and 3h) at 35 kHz frequency. Formed black precipitates were washed with distilled
prepared. To the cobalt and sulfur precursor solutions in the ultrasonic bath, 2% of 3-MPA was
added dropwise and ultrasonically stirred for different sonication times (1h, 2h, and 3h) at 35
kHz frequency at room temperature. Formed black precipitates were washed with distilled water
and ethanol. The formed black powder was heated at 100 ºC in air to study the effect of
annealing temperature.
3.1.Structural properties
The structure and particle sizes of the synthesized samples were characterized by a Bruker D2
Phaser X-ray diffractometer (XRD) using Ni-filtered Cu Ka radiation (λ = 1.54060 Å). The
structural properties of the samples synthesized at different sonication times and annealing
Nine high intensity diffraction peaks at 2θ =15.45°, 17.83°, 29.7°, 31.18°, 36.19°, 39,49°,
40.6°, 44.67° and 47.5° from {111}, {200}, {311}, {222}, {400}, {331}, {420}, {422}, and
{511} planes indicates of nanocrystalline Co9S8 particles. The average particle size of Co 9S8 was
(1)
where, D -is the diameter of the nanoparticle, λ -the X-ray wavelength is equal to 1.5418
Å and β is the half-width of the diffraction peak. The sonication reaction in aqua solution goes as
below:
The XRD results of cobalt sulfide nanoparticles obtained at different sonication times
(1h, 2h and 3h) using EG are shown in Fig.2. In this position, two mixed phases of Co 3S4
(linnaeite) and CoS2 (cattierite) nanoparticles were obtained in accordance with the JCPDS 00-
002-0825 and 00-003-0772, respectively. The diffraction peak at 2θ=20º corresponds to EG
amorphous phase.
In first hour sonication reaction Co3S4 nanoparticles were observed by 5 diffraction peaks
at 2θ =26,7°; 31,4°; 32,8°; 65,1° and 66° from {2 2 0}, {3 1 1}, {2 2 2}, {5 3 3} and {6 2 2}
planes. The second crystal phase of CoS2 was observed by 8 diffraction peaks at 2θ =36,5°;
40,03°; 46,3°; 49,3°; 54,9°; 57,6°; 63,2°; and 76,9° from {2 1 0}, {2 1 1}, {2 2 0}, {2 2 1}, {3 1
explained by the di-sulfidation and poly-sulfidation process. The XRD results of Co xSy/EG show
high-intensity peaks for in 1h reaction time (Fig. 2a) and low-intensity peaks for in 2 h reaction
time (Fig. 2b). In 3h reaction time all peaks completely disappeared and an amorphous phase
was observed (Fig.2c). The size of synthesized particles decreased by increasing sonication time.
The deceased crystallinity with increase in the sonication time could be due to the formation of
hot spots during the collapse of cavitation and physical stress due to the acoustic cavitation [25,
26].
Fig.2. XRD patterns of Co3S4/EG and/or CoS2/EG at different sonication time.
oxygen donor, and that the ligand can serve as a bidentate chelating as well as a monodentate
coordinating agent. Bidentate coordination is deduced for seven compounds and monodentate
coordination for eight compounds [27]. According to their work, the compound Co(EG)2X2 (X =
Cl, Br) can also be prepared by stirring the compound Co(EG)3X2 with sodium dried
diethylether. Then a dark blue syrup is formed, which solidifies after some time. The compound
Co(EG)2Cl2 can also be prepared by dissolving anhydrous CoCl2 (0.01 mole) in an equivalent
amount of the ligand (0.03 mole) [27]. Based on their opinion we can write the reaction:
) ) ) )
Co(CH3COO)2+3EG → Co(EG)3(CH3COO)2
) ) ) )
Co(EG)3(CH3COO)2 → Co(EG)2(CH3COO)2 + EG
) ) ) )
[Co(EG)2](CH3COO)2 → [Co(EG)2]2+ + 2CH3COO-
The XRD results of cobalt sulfide nanoparticles obtained using 3-MPA in 2h sonication
time and annealed at 100 ºC in air are shown in Fig.3. There are also two mixed phases of Co3S4
(linnaeite) and CoS2 (cattierite) nanoparticles were obtained. Co3S4 nanoparticles were observed
by 3 sharp diffraction peaks at 2θ = 26,7°; 31,4° and 38,3° from {2 2 0}, {3 1 1}, {4 0 0} planes.
The second crystal phase of CoS2 was observed by 4 diffraction peaks at 2θ = 32°, 36,5°; 46,3°
The crystallisation of nanoparticles was observed by sharp and precise signals. However, for
annealed CoxSy/3-MPA there is little oxidation process have been observed even at 100 ºC and
Co3(SO4)2(OH)2×(H2O)2 have been formed (Fig. 3). This oxidation process occurs at slightly
lower temperatures for in nano-size cobalt sulfide particles due to their large surface area. The
average particle size of Co xSy was calculated by the equation (1) was 30,03 nm before the
annealing and 15,88 nm after the annealing. It can be explained by the decreasing of
Using 3-MPA the sonochemical formation of the Co xSy may follow as below.
H2O ) ) ) )
→ H · + · OH
Adding 3-MPA to the solution the sonication process would result in formation of H 2S [28]
which is stimulates the initiation of the sulfidation process.
H · + · OH + HS-CH2-CH2-COOH ) ) ) )
→ H2S + HO-CH2-CH2-COOH
aq. solution
Co(CH3COO)2·4H2O → Co2+ + 2CH3COO- + 4H2O
H2S + Co2+) ) ) )
→ CoS + 2H+
The disulfidation and polysulfidation process goes in the system with increasing of sonication
time.
) ) ) )
nCoS → CoS2 (or CoxSy)
The cobalt polysulfides were substantially less reactive than either iron or nickel and
were evaluated as cathode materials in a lithium battery [24]. While the cobalt polysulfides are
nonconducting, the nickel equivalent is a good electrical conductor. The apparent stability of
these materials to air varies from metal to metal, with Co 2S7 appearing most stable, with no
apparent reaction to air, and Fe3S8 most reactive, turning orange in moist air and easily burning
in air [24].
3.2.Morphology by SEM.
Fig. 4 (A-D) and Fig. 5 (A, B) show SEM images of the cobalt sulfide nanoparticles into
particles synthesized at 2h sonication time show spherical morphology (Fig. 4A-D). The average
particle size was 170-200 nm, which is very higher than the value obtained from XRD analysis.
This is due to coalescing of smaller crystallites to form larger particles to lower Gibb's free
Fig. 4. SEM images (A); EDX spectrum (B) and mapping of images of cobalt and sulfur (C) of
When sonochemical synthesis was carried out for a long time, the particles were first
destroyed due to the long-term effects of ultrasound, and then combined together. Because, as
the particles decrease, they try to obtain a spherical structure. However, as the particles are
decreased, their surface energy increases, so they are combined with each other. Such a
combination has also led to the loss of the form, i.e. the occurrence of the fluctuations (Fig.
5A,B). By increasing the reaction time from 2h to 3h, due to long-term effects of ultrasound this
particle divided and have lost their spherical vision (Fig. 5A). It is shown that, besides the main
components (cobalt and sulfur) of NCs, in much smaller amounts of other elements, for example,
oxygen, carbon and so little amount of sodium were also detected (Fig. 4E and Fig. 5C ). We
accept that they are related to the precursor and surfactant because these elements are the main
Fig.5. SEM images (A); EDX spectrum (B) and mapping of images of cobalt and sulfur (C) of
3.3.Optical properties
temperature using UV-Vis and FTIR spectrometer. Band gap energy and transition type were
derived from mathematical treatment (2) of the data obtained from the optical absorbance versus
Where ν is the frequency, h is the Planck’s constant; k equals a constant while n carries the
value of either 1 or 4 [32, 33]. The optical band gap for each sample was obtained from the
intercept of the energy axis after extrapolation of the straight lines section of (αhν) 2 vs. hν curve.
Optical band gap of Co9S8/PVA is 1.81 eV, CoxSy/EG is 2.42 eV and CoxSy/3-MPA is 1.69 eV
given in Fig. 6 and Fig.7. The direct band gap of bulk cobalt sulfide is (0,78-0,9eV) [34].
Table 1.
Effects of sonication time and capping agent on the optical properties and particle size of CoxSy
NPs.
Chemical Capping Particle size (nm) Optical
composition agent and /or band
surfactant gap
1h sonication 2h sonication 3h sonication (eV)
time time time
Co9S8 PVA - 30 (by XRD) - 1.81
CoxSy (CoS2, EG 17.6 (by XRD) 11.7 (by XRD) Amorphous 2.42
Co3S4)
CoxSy (CoS2, 3-MPA 35.2 (by XRD) 30.03 (by XRD); Amorphous 1.69
Co3S4) 170-200 (by
SEM)
It is seen that the band gap increases, with decreasing of particle size, indicates the presence
of quantum confinement effect, consistent with the theoretical argument made by Brus [35]. The
wide bang gap indicates that synthesized nanocomposites can be used in the fabrication of
Fig.6. Absorbance spectra (A) and variation of (αhν)2 versus hν of Co9S8/PVA nanocomposites
(B).
Fig. 7. Absorbance spectra (A) and variation of (αhν)2 versus hν of CoxSy/EG (B) and CoxSy/3-
MPA(C) nanocomposites.
The FTIR spectra of Co 9S8/PVA nanocomposite obtained in different sonication time are
shown in Fig.8. and increasing or decreasing of some bands intensity as well as the shift of peak
Table 2
The characteristic band corresponding to OH group at 3408 cm-1 shift to 3367 cm-1 for 1h
sonication time and 3450 cm-1 for 2h sonication time upon the formation of Co 9S8. The shift in
the low-frequency is explained by the weakening of the chemical bond vibrations upon the
Also, to decrease in intensity and low-frequency shift of the peak of group (C-O) (from
1098 cm -1 to 1085 cm −1 for 1h and to 1024 cm −1 for 2h) can be explained by the same fact. The
peak at 3452 cm-1 (–OH) group in PVA shift to 3367 cm-1 and 3450 cm-1 frequencies in 1h and
2h sonication time, respectively. Shifting lower frequency at 1h reaction time and shifting higher
frequency at 2h reaction time can be explained by the fact that, cobalt sulfide nanoparticles
obtained at 1h sonication time on the functional group combined the PVA chain decrease the
oscillation of functional groups. At 2h sonication time, the long-term effect of ultrasound breaks
some chemical bonds between the polymer and nanoparticles, causes the increase of the
As can be seen from the Table 2 the S–S disulfide group corresponding to 480 cm-1
frequency [30, 39] has not been observed in the 1h reaction time (Fig. 8a). But in 2h reaction
time, the S–S disulfide group has observed at 497 cm-1 frequency (Fig. 8b). The polysulfides of
The FTIR spectra of Co xSy/EG nanocomposites obtained at different sonication time are
shown in Fig.9.
Fig. 9. FTIR spectroscopy spectra of CoxSy /EG nanocomposites obtained in different sonication
time: a) 1h; b) 3h
As can be seen from the Table 3 the S–S disulfide group corresponding to 480 cm-1
frequency has been observed even at 1h reaction time at 491 cm-1 frequency (Fig. 9a). It is also
observed from the XRD pattern of Co xSy/EG nanocomposites synthesized for 1h reaction time
(Fig.2). This result can be explained that the functional groups of EG are more reactive than
PVA. The intensity of S-S polysulfide bond decreased with increasing reaction time from 1h to
Table 3
sonication time and annealed at 100 ºC in the air are shown in Fig.10. The increasing or
decreasing of some bands intensity, as well as the shift of peak position, are shown in
Table 4. It is determined that the intensity of some bands of 3-MPA into nanocomposites
has been decreased and disappeared after annealing at the temperature. It occurs in
4. Conclusions
the liquid phase synthesis of the sonochemical method using PVA, EG and 3-MPA as a capping
agent and surfactant. Two mixed phases of Co 3S4 (linnaeite) and CoS2 (cattierite) nanoparticles
were obtained using EG and 3-MPA. The superiority of nanoparticles formed in CoS 2 phase is
explained by the di-sulfidation and poly-sulfidation process. The XRD results of Co xSy/EG show
high-intensity peaks for in 1h reaction time, low-intensity peaks for in 2 h reaction time. In 3h
reaction time, all peaks that correspond to cobalt sulfide crystalline phase, completely
disappeared and an amorphous phase was observed. The synthesized particles decreased by
increasing sonication time. The particles synthesized at 2h sonication time show spherical
morphology. By increasing the reaction time from 2h to 3h, due to long-term effects of
ultrasound this particle divided and have lost their spherical vision. The characteristic band
corresponding to OH group at 3408 cm-1 shift to 3367 cm-1 for 1h sonication time and 3450 cm-1
for 2h sonication time upon the formation of Co 9S8 nanoparticles. The low-frequency shift is
explained by the weakening of chemical bond vibration upon the formation of Co 9S8
nanoparticles. It is determined that after annealing of samples the intensity of some bands of 3-
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HIGHLIGHTS
CoxSy nanoparticles with CoS2 and Co3S4 content were obtained using EG and 3-MPA.
The oxidation occurs at low annealing temperature due to large surface area of NPs.