Accepted Manuscript

Synthesis and characterization of cobalt sulfide nanoparticles by sonochemical

method

Mustafa B. Muradov, Ofeliya O. Balayeva, Abdulsaid A. Azizov, Abel M.

Maharramov, Lala R. Qahramanli, Goncha M. Eyvazova, Zohrab A.
Aghamaliyev

PII: S1350-4495(17)30203-7
DOI: https://doi.org/10.1016/j.infrared.2018.01.014
Reference: INFPHY 2472

To appear in: Infrared Physics & Technology

Received Date: 16 April 2017

Revised Date: 7 December 2017
Accepted Date: 11 January 2018

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

Mustafa B. Muradovb, Ofeliya O. Balayevaa*, Abdulsaid A. Azizova, Abel M. Maharramova,

Lala R. Qahramanlib, Goncha M. Eyvazovab, Zohrab A. Aghamaliyevb

a
Department of Chemistry, Baku State University, Z. Khalilov str., 23, AZ-1148 Baku, Azerbaijan
b
Department of Physics, Baku State University, Z. Khalilov str., 23, AZ-1148 Baku, Azerbaijan

ABSTRACT

Convenient and environmentally friendly synthesis of Co9S8/PVA, CoxSy/EG and

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

morphology of nanocomposites were characterized using X-ray diffractometer (XRD),

Ultraviolet/Visible Spectroscopy (UV-Vis), Fourier-transform infrared spectroscopy (FTIR) 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

properties of the nanoparticles have been studied in detail.

Keywords: nanocomposites (NCs); sonochemical synthesis; optical properties; capping agent

* Corresponding author (O.O.Balayeva).

Tel.: +994 515 765 875

E-mail address: ofeliya1989@inbox.ru

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,

abundant (the principal component of natural gas) and environmentally friendly.

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

nanocrystalline Co3S4 nanoparticles through a hydrothermal reaction with different

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

cells possessed high gravimetric and volumetric energy densities [24].

In this work, cobalt sulfides/PVA, cobalt sulfides/EG, and cobalt sulfides/3-MPA powder

nanocomposites were synthesized by a sonochemical method. Co9S8 nanoparticles were obtained

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

2.1. Materials and instrumentation

Cobalt sulfide nanoparticles were synthesized in the presence of ultrasonic irradiation by the

liquid phase synthesis of the sonochemical method. All chemicals [Co(CH3COO)2·4H2O,

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.

2.2.Preparation of cobalt sulfide/PVA NCs

20 ml 0.46 M of Co(CH3COO)2·4H2O and 20 ml 1.125 M of Na2S·9H2O water solutions were

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.

2.3.Preparation of cobalt sulfide/EG NCs

3.5 g of Co(CH3COO)2·4H2O and 4.8 g of Na2S·9H2O were separately added to 20 ml EG and

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

water and ethanol and air dried.

2.4.Preparation of cobalt sulfide/3-MPA NCs

25 ml 0.128 M of Co(CH3COO)2·4H2O and 30 ml 0.5 M of Na2S·9H2O water solutions were

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. RESULTS AND DISCUSSION

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

temperature are shown in Fig 1. According to JCPDS-00-002-1459, Co9S8 nanoparticles in cubic

phase has been identified.

 Fig.1. XRD pattern of Co9S8/PVA sonicated for 1 h.

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

calculated by the Debye-Scherrer’s equation (1) is 30 nm.

(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:

Co(CH3COO)2·4H2O aq. solution → Co2+ + CH3COO- + 4H2O

Co2+ +S2- → CoS

) ) ) )
nCoS → CoS2 (or CoxSy)

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

1}, {2 2 2}, {3 2 1} və {0 2 4} planes. 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 (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.

Na2S×9H2O + H2O → 2Na2+ + S2- +10HOH

) ) ) )
H2O → H. + .OH

D. Knetsch and W. L. Groeneveld shows that ethylene glycol behaves as a normal

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-

[Co(EG)2]2+ + 2S2- + H. + .OH ) ) ) )

→ [Co(EG)2]S + CoS + EG + H2 + H2O2
) ) ) )
nCoS → CoS2 (or CoxSy)

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°

and 57,6° from {2 0 0}, {2 1 0}, {2 2 0} and {2 2 2} planes.

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

nanoparticles size at the temperature.

Fig. 3. XRD pattern CoxSy/3-MPA at different annealing temperature

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

CoxSy/3-MPA nanocomposites synthesized at 2h and 3h sonication times, respectively. The

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

energy [29, 30].

Fig. 4. SEM images (A); EDX spectrum (B) and mapping of images of cobalt and sulfur (C) of

CoxSy/3-MPA nanocomposites synthesized at 2h sonication time.

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

components of them [31].

Fig.5. SEM images (A); EDX spectrum (B) and mapping of images of cobalt and sulfur (C) of

CoxSy/3-MPA nanocomposites synthesized at 3h sonication time.

3.3.Optical properties

3.3.1. UV-Vis spectroscopy study

The optical properties of synthesized nanocomposites were measured at room

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

wavelength data with the following relationship for near-edge absorption:

A = [k(hν – Eg)n/2] / hν (2)

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

optical and photonic devices.

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.

3.3.2. FTIR spectroscopy study

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

position is shown in Table2.

Table 2

FTIR spectroscopy characterization of Co9S8/PVA nanocomposites.

Functional The characteristic Frequences in different

 groups and bonds absorption signals (cm-1) sonication time (cm-1)
1h 2h

C-H 2945 - 2943

-CH2 854 775 833
OH 3408– 3391 3367 3450
C-O 1098 1085 1024
C-O-H 1371 - 1374
C–C and C–O–C 1135 - 1131
S-S 480 - 497

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

formation of Co 9S8 nanoparticles [36-38].

Fig. 8. FTIR spectroscopy spectra of Co9S8 /PVA nanocomposites obtained in different

sonication time: a) 1h; b) 2h

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

oscillation of the functional groups and shifting higher frequency.

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

cobalt has been obtained with increasing sonication time.

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

3h. (Fig. 9b).

Table 3

FTIR spectroscopy characterization of CoxSy/EG nanocomposites.

Functional The characteristic Frequences in different sonication

groups and absorption signals time (cm-1)
bonds (cm-1) 1h 3h

C-H 2878 2958 -

1343 1317 1374
C-O-H 1094 1078 1088
OH 3441 3400 3446
C-O 1240 1235 1242
The FTIR spectra of cobalt sulfide nanoparticles obtained using 3-MPA at 2h

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

connection with the decomposition and evaporation of 3-MPA at high temperature.

Fig. 10. FTIR spectra of CoxSy /3-MPA nanocomposites: a) air dried; b)annealed at 100ºC in air

Table 4. FTIR spectroscopy characterization of CoxSy/3-MPA nanocomposites.

Functional groups The characteristic Frequences in 2h Frequences at 100ºC

and bonds absorption signals (cm-1) sonication time (cm-1) air annealing (cm-1)
-OH (-COOH) 3030 3277 -
-C=O 1730 1733 1736
S-C 876 836 843
C-O 1300 -1000 1300 -1000 1300 -1000
C-H 1340 1291 1259

4. Conclusions

Cobalt sulfide nanoparticles were synthesized in the presence of ultrasonic irradiation by

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-

MPA has decreased and disappeared.

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HIGHLIGHTS

CoxSy nanoparticles with CoS2 and Co3S4 content were obtained using EG and 3-MPA.

CoxSy/EG show high-intensity peaks in 1h, low-intensity peaks in 2 h reaction time.

The oxidation occurs at low annealing temperature due to large surface area of NPs.

At 3h sonication time particles divided due to long-term ultrasound effects.