Materials Research Express

PAPER

Cobalt nanoparticles synthesis by cobalt nitrate reduction

To cite this article: Ella L Dzidziguri et al 2019 Mater. Res. Express 6 105081

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 Mater. Res. Express 6 (2019) 105081 https://doi.org/10.1088/2053-1591/ab3ca8

PAPER

Cobalt nanoparticles synthesis by cobalt nitrate reduction

RECEIVED
1 May 2019
REVISED
Ella L Dzidziguri, Elena N Sidorova, Marzhan Inkar, Andrey G Yudin, Elena V Kostitsyna,
12 August 2019 Dmitriy Yu Ozherelkov, Konstantin V Slusarsky, Anton Yu Nalivaiko and Alexander A Gromov
ACCEPTED FOR PUBLICATION National University of Science and Technology MISiS, Moscow, 119049, Moscow, Leninskiy Avenue 4, Russia
19 August 2019
E-mail: [email protected]
PUBLISHED
30 August 2019 Keywords: metals, oxides, nanostructures, chemical synthesis, reduction mechanism, magnetic properties

Abstract
The paper describes the synthesis of cobalt nanoparticles in alkali solutions. Co nanoparticles were
synthesized by the chemical reduction of a Co(NO3)2 salt alkali solution. The process was followed
by hydrogen reduction at high temperature for 30–150 min The TGA and XRD analysis of the
obtained samples was carried out. The characteristic size of the particles on each stage of the
process was defined as well as its phase composition. The morphology and particle size distribution
of the obtained samples were also defined. The dependence of coercive force and saturation
magnetization on the diameter of the obtained nano-sized particles were measured as well. The
saturation magnetization was found to be constant for particles larger than 40 nm. The reduction
scheme for Co nanoparticles was proposed based on experimental results obtained. The average
size of the Co nuclei in samples was defined to be 2.9 nm and didn’t change with reduction
time. The presence one-molecule water film on the surface of Co nuclei was found on the
TEM-images.

1. Introduction

Nanomaterials and, especially, nanoparticles represent one of the most important fields of modern materials
science [1–4]. The properties of the synthesized nanomaterials depend on the chemical composition and
production methods, size, morphology, and structure of the obtained particles. Co is an important inorganic
material for a wide range of applications [5–11]. Among magnetic nanoparticles, Co nanoparticles have a
significant saturation induction. They are also the perspective materials for magnetic fluids development [12],
microwave absorbers [13–15], information storage devices [16, 17] and in the biomedical area [18, 19].
Several methods were applied for Co nanoparticles synthesis [20–22]. The most common methods for those
synthesis are: chemical reduction of oxides [5–7], evaporation-condensation methods [21, 23] sol-gel [24, 25],
plasma-chemical synthesis [7], and biosynthesis [26].
Chemical methods are widely used for Co nanoparticles production despite their multistage character. These
methods are characterized by technological simplicity, as well as by the ability to control the synthesis process at
each stage by varying the synthesis conditions (temperature, pH, concentrations of reagents, etc). The
parameters of the synthesis can be varied for obtaining the final nanoparticles with required properties such as
phase composition, dispersity, and morphology.
Co nanoparticles can be obtained by the chemical reduction of salts in alkali solutions, followed by hydrogen
reduction. However, the influence of the synthesis conditions on the properties of the obtained nanoparticles,
such as particle size distribution and phase composition, is still unclear.
The purpose of this work is to study the reduction scheme of the oxygen-containing cobalt compounds and
the influence of particle’s shape and morphology of the initial Co salt on the particle size distribution and
morphology of the obtained cobalt nanoparticles.

© 2019 IOP Publishing Ltd

Mater. Res. Express 6 (2019) 105081 E L Dzidziguri et al

Figure 1. NANOCHIM equipment scheme.

2. Materials and methods

2.1. Materials
The (Co(NO3)2·6H2O) and NaOH with 99.9 wt. % purity (purchased from REAHIM Ltd) were used as initial
precursors for the Co(OH)2 nanoparticles synthesis. The 500 ml of 10 wt. % salt of (Co(NO3)2·6H2O) in alkali
solution were prepared for the synthesis process.

2.2. Synthesis procedure

The Co(OH)2 was synthesized via chemical precipitation method using synthesis complex NANOCHIM Ltd
Functional Nanomaterials. The NANOCHIM equipment scheme is shown in figure 1. The NANOCHIM
multicomponent equipment consists of PC, thermostat - Lauda ECO Silver RE 420, mixer - Heidolph RZR 2051
control, peristaltic pumps - Heidolph Pumpdriver 5201, pH-Meter—Mettler Toledo MP 230 and reactor. The
temperature was maintained in the reactor at 10 °С. The initial salt and alkali solutions were fed into the reactor
by the peristaltic pumps. The pH level was maintained between 8 and 9. The mixer was shuffled the colloid at
700 rpm. The obtained Co(OH)2 was washed in distilled water and after that in ethanol to obtain Co(OH)2 (1)
Co (NO3 )2 + 2Na (OH )  Co (OH )2 + 2NaNO3 (1)
The washed cobalt hydroxide was dried via lyophilization in the Christ Alpha 1-2 LD plus dryer. The sample
of CoO was obtained via Co(OH)2 calcination in the muffle furnace SNOL 6/12 at 400 °C (for a comparison) (2)
Co (OH )2  CoO + H2 O (2)
Metallization temperature was chosen based on TGA data. The cobalt hydroxide was metallized by reaction (3)
CoO + H2  Co + H2 O (3)

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Figure 2. Thermogravimetric curve for cobalt hydroxide sample during reduction at 220 °C.

Metallization was carried out in the tube furnace Carbolite HZS 12/600 E in a quartz reactor of 1000 mm
length and 100 mm in diameter, at 220 °С with various metallization time 30, 60, 90, 100, 105, 110, 115, 120,
150 min in H2 atmosphere. The initial Co(OH)2 weight for all metallized samples was equal to 5 g. H2 flow rate
was kept stable at 12 l min−1.
The Co(OH)2 reduction time was determined by non-isothermal heating in H2 medium via SDT Q-600
thermal analyzer (TA Instruments, USA). The qualitative and quantitative phase analysis of the samples was
executed by the x-ray diffractometer ‘Difrey 401’ (Russia). The magnetic properties of the reduced samples were
investigated by vibrational magnetometry method via the VMA-1 (Russia). For each sample, two series of
measurements of magnetic properties were carried out.
The morphology and particle size distribution of the initial Co(OH)2 and obtained Co nanoparticles were
studied by both JEM-6700F scanning electron microscope and JEM-2100 transmission electron microscope
(JEOL, Japan). The average particle size of Co(NO3)2 samples as well as the average particle size of the Co(OH)2
and the resulting metallic Co particles were defined from SEM images.

3. Results and discussion

3.1. Particle morphology and size distribution

According to TGA (figure 2) the average reduction time of cobalt hydroxide was 95 min at 220 °C. The
temperature of 220 °C was chosen on the basis of the experimental results.
From the results of TGA, the reduction process conditions were determined as follows: temperature 220 °С
and various values of reduction time 30–150 min.
According to the XRD data, the reduced samples were consisted of several phases: α-Co, β-Co and CoO
(figure 3, table 1). The α-Co phase content was increased and the β-Co and CoO content was decreased with the
recovery time. The presence of a small amount of CoO phase can be explained by the fact that the oxide phase
was formed in the particle’s nucleis during the reduction. The reduced samples have a large amount of Co phase.
Thus, for these 2 samples (which were reduced for 115 and 120 min) the reduction was complete
The average particle size was increased to 44 nm with an increase in the temperature and reduction time as
well as density of Co nucleis (up to 332). While the amount of nucleis was being increased linearly with reduction
time their average diameter growth obviously slowed down after 100 min The average sample size (for samples
with reduction time below 110 min) was less than 40 nm. These samples were not fully recovered (see table 1).
The average sizes of the metallic cobalt nanoparticles did not change with an increase in the isothermal time of
reduction.
The Co(OH)2 was crystallized as platelet particles according to SEM (figure 4(a)). According to XRD, the
calcination products of Co(OH)2 was consisted of the cobalt oxide phase, obtained under reaction (1). TEM
results showed that dehydration occurs within the hydroxide particles (figure 4(b)).
The average diameter and thickness of the Co(OH)2 and CoO particles are presented in table 2. During the
dehydration process, neither the shape nor the size of the initial hydroxide particles were changed, CoO exists
within the particles formed by the precipitation of the hydroxide.
The TEM showed that in the oxide particles, the nuclei of the metal phase were formed. The number of Co
nucleis increased with the reduction time while the average size of each nuclei was 2.3 nm and remained
unchanged (figure 5). A small amount of metal cores were found in the material which was recovered for 30 min

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Figure 3. The x-ray diffraction of cobalt nanopowder after reduction at 220 ° C and various reduction times.

Figure 4. TEM-images: (a) Co(OH)2; (b) CoO.

Table 1. Results of XRD quantitative phase analysis and the diameters of obtained nanoparticles calculated from TEM data.

Reduction Phase content, wt.% Average nanoparticle dia- Average amount of nuclei per unit of surface
time, min meter, nm area (per square of 50×50 nm)
α-Со β-Со CoO Co3O4

30 0 0 23 77 <1 188
60 0 0 42 58 18 213
90 25 12 38 25 27 242
95 32 14 54 0 32 255
100 49 17 34 0 35 261
105 52 16 32 0 37 274
110 77 14 9 0 39 278
115 78 13 9 0 42 296
120 81 11 9 0 43 298
150 85 7 8 0 44 332

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Mater. Res. Express 6 (2019) 105081 E L Dzidziguri et al

Figure 5. TEM images of reduced Co samples (see table 1) at the certain time, min: (a) 30 (b) 60 (c) 90 (d) 110 (e) 115.

Figure 6. TEM-image of the synthesized cobalt hydroxide.

Table 2. Dimensional characteristics of

the cobalt hydroxide and cobalt oxide
platelet particles.

Average size, nm
Sample
diameter thickness

Co(OH)2 245 55
CoO 237 54

(figure 5(a)) which were linearly increased with reduction time (figure 5(a)–(c)). At the reduction time of
110 min, the particle had consisted of small metal nucleis (figure 5(d)). Finally, the small metal particles had
started to coagulate and formed large metal particles at the reduction time of 115 min (figure 5(e)). The sample
coagulation occurred only after the entire particle consisted of small metallic nuclei. Also, the TEM showed that
the morphology of Co(OH)2 was relatively unchanged until the large metal particles were formed in the samples.
The morphology of the material was changed in the reduced samples consisting of coagulated metal particles.

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Figure 7. The dependence of coercitive force and saturation magnetization on particle diameter of partially and completely reduced
Co samples.

Figure 8. x-ray diffraction pattern of samples obtained at 30 (a) and 150 (b) min of reduction.

Table 3. Magnetic characteristics of cobalt nanopowder.

Reduction time, min MS, A·m2/kg Mr, A·m2/kg MS/Mr

30 1 0 0
60 6 2 0.31
90 60 22 0.36
95 71 27 0.37
100 83 31 0.37
105 103 38 0.37
110 132 51 0.39
115 141 56 0.39
120 143 58 0.41
150 143 58 0.41

Figure 6 shows the partial coagulation of nuclei within a single particle of Co(OH)2. The diameter
measurement results of metallic cobalt particles from TEM micrographs are shown in table 1.
The change in metallic cobalt phase was confirmed by the results of magnetic studies. Magnetic studies
showed that the saturation magnetization of the cobalt nanoparticle increased steadily with an increase in the
average particle diameter up to 40 nm (figures 7 and 8). The saturation magnetization value did not change with
the average particle diameter value above 40 nm (table 3). Maximal mass of Co particles formed per minute of
reduction time was found to be at regime with 115 min The coercive force, as opposed to saturation
magnetization, is a structurally sensitive property. The inhomogeneous phase composition complicates the
motion of magnetic domain boundaries and increases the coercive force. When the particle diameter reached
30 nm the coercive force gradually decreased which is associated with an increase α–Co phase in the cobalt
nanoparticles (figure 7).

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The minimums of the saturation magnetization (Ms) and residual magnetization (Mr) were observed for the
sample obtained at a 30-minute reduction time. The Ms and Mr were increased with the enlargement of the
metallic cobalt phase size.
This may be due to the fact that in the samples, the particle amount decreased in the superparamagnetic
state. The rectangularity coefficient Ms/Mr increased to the moment of nuclei coagulation, reaching a value
close to the maximum. The maximum possible value of the rectangularity coefficient Ms/Mr for arbitrarily
oriented particles was 0.48.

3.2. The reduction scheme

The final stage of Co nanoparticles production was the reduction process. Reduction process referred to a gas-
solid system. The substance was transported by a gas-liquid phase with a movable surface. This process was
called the ‘shrinking core’. During the reaction, a solid phase was formed in addition to the gaseous substance.
The formed solid phase defined the consumption of the solid reagent. During the process, the size of the solid
particle did not change. A gas stream containing a reagent flowed around a solid particle. There was the
boundary layer surrounding the particle. The mass exchange between the gas flow and the surface of the solid
passed through this layer. The reaction began on the surface of the solid and moves inward. After a certain time,
the particle consisted of a nucleus and an outer layer of the reaction product. The unreacted product was
concentrated in the core. During the reaction, the nucleus decreases, whereas the particle size remained
the same.
It was assumed that cobalt nanoparticle nucleation and growth will occur according to the described above
scheme. However, the results had shown a different process.
Based on the obtained data and calculations, the scheme of the cobalt hydroxide reduction was proposed.
The oxide phase collected in the aggregates was formed within the initial hydroxide particle. This phase had
the same diameter and thickness of the initial cobalt hydroxide particle. In these oxide particles, the nuclei of the
metal phase were formed and the number of oxide particles and were increased with the recovery time. During
the reduction process, these small nuclei of the metallic phase were coagulated into larger ones and formed large
metallic cobalt particles.
According to the obtained microphotographs, the mechanism of nuclei and metal particle formation of all
samples was identical, while all differences on SEM images were caused by different reduction times.
As a hypothesis of the coagulation absence (or nuclei growth), the assumption could be made about the
formation of a water layer around each nuclei. The products of the oxide reduction reaction were metal and
water. The metal atoms formed small nuclei. The water molecules were enclosed in the capillary between an
oxide layer and metal which constrains water molecule diffusion from the particle. The metallic Co nuclei
coagulation occurred after the elimination of water molecules from the samples.

4. Conclusions

The Co nanoparticles were obtained by the chemical reduction of CoO. The average size of the obtained Co
nanoparticles didn’t change until the coagulation stage. The average size of the fully reduced metallic Co particles
was∼43 nm and it didn’t increase with the isothermal reducing time while their amount was found to linearly
increase. The optimal regime for the maximal mass of Co particles formed was identified at 115 min
reduction time.
The values of saturation magnetization and residual magnetization were increased with the size of Co
nanoparticles, which was associated with a decrease in the number of particles in the superparamagnetic state.
The saturation magnetization increased up to 145 G·cm3 g−1 with particle diameter and stayed constant for
larger particles.
The scheme of particle formation during the reduction process of Co(OH)2 by the H2 was proposed. Co
nanoparticles were formed by the agglomeration from the one initial Co(OH)2 particle by the proposed scheme.
The proposed hypothesis is that there is no coagulation or growth of the Co nuclei of water surrounding each
nuclei.

Acknowledgments

The work is financially supported by Russian Scientific Foundation (RSF) grant № 19-79-30025.
The authors thank the MISIS Academic Writing Center for its assistance in the preparation of this
manuscript.

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ORCID iDs

Anton Yu Nalivaiko https://orcid.org/0000-0003-2475-4811

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