Article

Journal of
Copyright © 2019 American Scientific Publishers
Nanoscience and Nanotechnology
All rights reserved Vol. 19, 453–458, 2019
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The Synthesis and Use of Nano Nickel Catalysts

Adél Anna Ádám1 2 , Márton Szabados1 2 , Ádám Polyákovics2 , Katalin Musza1 2 , Zoltán Kónya3 4 ,
Ákos Kukovecz3 , Pál Sipos2 5 , and István Pálinkó1 2 ∗
1
Department of Organic Chemistry, University of Szeged, Dóm tér 8, Szeged, H-6720, Hungary
2
Material and Solution Structure Research Group, Institute of Chemistry, University of Szeged,
Aradi Vértanúk tere 1, Szeged, H-6720, Hungary
3
Department of Applied and Environmental Chemistry, University of Szeged, Rerrich B. tér 1, Szeged, H-6720, Hungary
4
MTA-SZTE Reaction Kinetics and Surface Chemistry Research Group, Rerrich B tér 1, Szeged, H-6720, Hungary
5
Department of Inorganic and Analytical Chemistry, University of Szeged, Dóm tér 7, Szeged, H-6720, Hungary

The hydrazine reduction method was applied for the synthesis of nickel nanoparticles without using
inert atmosphere and added surface active agents. The effect of the preparation temperature and
the chemical quality of the metal sources as well as the solvents were studied. The generation of
nanoparticles were studied primarily by X-ray diffractometry, but scanning and transmission elec-
tron microscopies as well as dynamic light scattering measurements were also used for the better
understanding of the nanoparticles behaviour. The elevation of temperature was the key point in
transforming Ni(OH)2 into metallic nickel. By selecting the metal source, the obtained crystallite
sizes could be tailored between 7 nm and 15 nm; however, the SEM and DLS measurements
IP: 79.110.19.190
revealed significant agglomeration On:inWed,
resulting 05 Decwith
aggregates 2018 20:11:43
spherical or Ni(OH)2 resembling
Copyright: American Scientific Publishers
morphologies depending on the solvent used. The catalytic activities of the nanoparticles prepared
Delivered by Ingenta
were tested and compared in a Suzuki-Miyaura cross-coupling reaction.
Keywords: Ni Nanoparticles, Hydrazine Reduction, XRD-SEM-TEM-DLS, Suzuki-Miyaura
Cross-Coupling.

1. INTRODUCTION gas-phase photonucleation12 and other methods, such as

In recent decades, nickel nanoparticles (NPs) have received
significant attention in the material science research com-
munity, due to their extraordinary physical, electrical, opti-
cal and chemical properties as the consequence of the
increased surface to bulk atomic ratio.1 2 These attributes
depend strongly on the size and shape of NPs, there-
fore numerous synthetic methods were developed for
their controlled production. Chemical reduction is the
most frequently used route, where a strong reducing
agent, for instance polyol,3 supercritical alcohols,4 hydro-
gen gas,5 hydrazine,6 7 metal hydrides8 9 are applied to
obtain nickel NPs from dissolved nickel salts. These meth-
ods usually offer high mass production and well-tailored
nano- and microstructures under relatively mild condi-
tions. However, chemical reduction is not always feasi-
ble, therefore many physical methods like thermal plasma
synthesis,10 mechanochemical technique,11 laser-assisted
∗
Author to whom correspondence should be addressed.
electro-13 and sonochemical depositions14 and pyrolysis15
have been published in relation with the synthesis of nickel
fine powders and nanoparticles.
Nanometals find wide-ranging applications from
catalysis,16 which can be regarded as the most intensely
investigated area, through photochemistry,17 medicine18 to
electronics.19 Nobel metal NP catalysts have high density
of states (DOS) near their Fermi levels,20 high chemical
activities and stabilities, therefore, they gained increased
attention in practical applications in recent years.21 In the
meantime, the commonly researched and used noble met-
als, such as platinum, palladium, silver, or gold, became
scarcer and thus more and more expensive, the more
accessible transition metals like Ni, Cu, Fe, Co could be a
suitable and economical alternative in chemical processes.
To the best of our knowledge, this is the first report for
the synthesis of nickel NPs directly from nickel hydroxide
and a nickel complex based on the hydrazine reduction
method in ethanol-water mixture without surface-active

J. Nanosci. Nanotechnol. 2019, Vol. 19, No. 1 1533-4880/2019/19/453/006 doi:10.1166/jnn.2019.15781 453

The Synthesis and Use of Nano Nickel Catalysts Ádám et al.

additive and O2 -free atmosphere. Applying this technique, In the second step, the direct reduction of nickel hydrox-
the first step is the dissolution of the nickel salt and the ide particles to nickel NPs took place in hydrazine solution
precipitation of hydroxide by adding alkali. The second with or without ethanol addition. Beside the lack of alkali,
step is the reduction of the hydrazine on the surface of the the reduction conditions were the same as in the synthesis
precipitates. Our further aim was to investigate the effect starting from nickel chloride. The molar ratio was 10 for
of the synthesis temperature and the elimination of the N2 H4 /Ni2+ , and the solution was stirred at 50  C for 1 or
first step, i.e., the reduction of nickel hydroxide powder to 4 h. The black precipitate was filtered and stored under
metal NPs in ethanolic and aqueous medium directly. For- acetone in inert atmosphere.
mation of the nanoparticles were mainly studied by X-ray
diffractometry (XRD), but the obtained samples were char- 2.4. The Synthesis of NiNPs from
acterized by dynamic light scattering (DLS), scanning Tetraethylammonium Tetrachloronickelate
(SEM) and transmission (TEM) electron microscopy mea- ([(C2 H5 )4 N]2 NiCl4 )
surements as well. The synthesis route followed the procedure of direct
The catalytic activity of the nanoparticles prepared were nickel hydroxide reduction. The tetraethylammonium
studied in the Suzuki-Miyaura cross-coupling reaction of tetrachloronickelate complex was synthesized following
aryl halide and arylboronic acid,22 and compared to com- the a study of Lopez-Salinas et al.23 The complex pre-
mercial nickel powder and nickel nanoparticles generated pared (2.9 g) was added to absolute ethanol (12.5 cm3 
from nickel chloride by the unmodified method.7 and mixed with the already described ethanolic hydrazine
and the base at 50  C and stirred for 4 h. Finally, the black
precipitate was collected and protected from O2 in the way
2. EXPERIMENTAL DETAILS
described already.
2.1. Materials
All reagents and solutions applied in these experiments 2.5. Procedure for the Suzuki-Miyaura
were of reagent grade and used without further purifi- Cross-Coupling Reaction
cation. Metallic nickel (99.7% purity, average diameter
The catalytic tests were carried out in a 5 cm3 glass
<50 m), nickel chloride hexahydrate (NiCl2 × 6H2 O),
reactor immersed into a preheated oil bath using hot
>78 wt% hydrazine monohydrate (N2 H4 × H2 O) solution,
plate magnetic stirrer. Aryl halide (4 -bromoacetophenone)
potassium hydroxide (KOH), 4IP: 79.110.19.190 On:
-bromoacetophenone andWed, 05 Dec 2018 20:11:43
Copyright: (1.0 mmol),
American Scientific arylboronic acid (phenylboronic acid)
Publishers
phenylboronic acid were purchased from Sigma-Aldrich.
Delivered by(1.2 mmol), base (2.5 mmol of anhydrous pyridine) and
Ingenta
Absolute ethanol, toluene, pyridine, octanol and acetone metallic nickel catalyst (9.6 mg) were stirred with 3 cm3 of
were obtained from VWR International. solvent (anhydrous toluene) at 90  C in air. At the end of
the reaction, the obtained suspension was filtered, and the
2.2. Synthesis of NiNPs from Nickel Chloride clear liquid was injected into the gas chromatograph (GC)
In the first step, nickel chloride (0.7 g) was dis- to determine the conversion using 1-octanol as the internal
solved directly in absolute ethanol (12.5 cm3 . In paral- standard. The GC was a Hewlett-Packard 5890 Series II
lel, in another vessel solid potassium hydroxide (1.6 g, instrument equipped with 50-m-long Agilent HP-1 column
KOH/Ni2+ ratio was 10) and hydrazine monohydrate and flame ionization detector. The heating was set in stages
(1.4 g, N2 H4 /Ni2+ was 10) were mixed in 12.5 cm3 from 90  C to 350  C, and the chromatographic peaks were
of ethanol. The nickel chloride solution and the base- identified applying authentic samples.
hydrazine-ethanol mixture were mixed and stirred at
25  C, 50  C or 75  C for 4 h. The obtained precip- 2.6. Methods of Structural Characterization
itates were collected on a 0.45 m filter, washed by For registering the powder X-ray diffractograms, a Rigaku
deionized water and acetone. Until characterization, the Miniflex II powder X-ray diffractometer was applied in the
particles were stored under acetone in oxygen-free (N2   = 5–80 range with 4 /min scan speed using CuK ( =
atmosphere. 15418 Å) radiation. To identify the reflections of the NPs,
the JCPDS (Joint Committee of Powder Diffraction Stan-
2.3. Preparation of NiNPs from Nickel Hydroxide dards) database was utilized. The average crystal sizes of
In this synthesis, the above-mentioned procedure was sep- the particles prepared were calculated from the full width
arated into two steps. First, the precipitation of nickel at half maximum of the most intense reflection of metal-
hydroxide occurred in the reaction of dissolved nickel lic nickel applying the Scherrer equation using 0.9 as the
chloride (0.7 g in 25 cm3 absolute ethanol) and solid potas- shape factor, after fitting Gaussian curve on the reflection
sium hydroxide (1.6 g). Then, the mixture was stirred for measured.
1 h under 25  C, and the green precipitate was filtered, The morphology and the size of the nanocrystals were
washed by deionized water and dried at room temperature examined by scanning electron microscope (SEM–Hitachi
for 48 h in air. S-4700 instrument) and transmission electron microscopy

454 J. Nanosci. Nanotechnol. 19, 453–458, 2019

Ádám et al.
(TEM–FEI TECNAI G220 X-TWIN instrument) at various
magnifications at 10 kV and 200 kV acceleration voltages,
respectively. For sharper SEM imaging, the particles were
coated with few nanometers of gold layer, and the elemen-
tal analysis was performed with energy dispersive X-ray
analysis (EDX) measurements (Röntec QX2 spectrometer
equipped with Be window and coupled to the microscope).
A Malvern NanoZSD dynamic light scattering (DLS)
instrument, installed with a 4 mW helium-neon laser light
source ( = 633 nm), was applied to map the size distri-
bution of the samples at room temperature. For the DLS
measurements, the detection was performed in back scat-
tering mode at 173, and the nanoparticles were dispersed
in ethylene glycol with 1 h ultrasonic irradiation. The par-
ticle concentration was 2 mg/mL.
3. RESULTS AND DISCUSSION
3.1. Nanoparticles Studied by X-ray Diffractometry
The formation of metallic nickel was followed and veri-
fied via the X-ray diffractograms of the samples prepared.
Firstly, the effect of synthesis temperature was investigated
using the nickel chloride source (Fig. 1), and it was proved
to be a crucial parameter. At room temperature there was
no sign of nickel nanoparticles, the reflections (JCPDS#74-
2075) of hydroxide solid (i.e., the hydrolysis of the nickel
chloride took place) was only observable. The Ni(OH)2
was very stable at 25  C, the hydrazine
IP: 79.110.19.190
molecules On:wereWed,the
unable to reduce it in 4 h, but 24 h wereCopyright: American
sufficient to gener- Scientific
ate metallic nickel. On elevating the temperature,Delivered
the gen- bypared
eration of nickel (JCPDS#04-0850) nanoparticles became
possible, and phase-pure solid material was obtained in
4 h. Only three reflections were noticed, (111), (200),
(220) they were, indicating pure face-centered cubic (fcc)
structure. Since the crystallite sizes remained practically
constant up to 75  C, further synthetic work was carried
out at 50  C.
To examine the effect of the quality of the nickel-
containing reactants, which may have direct or indirect
(111)
17 nm
(200)
(220)
75ºC
Intensity / a.u.
15 nm
50ºC
(100)(011) (110)
(001) (012)
25ºC
10 20 30 40 50
2θ / º
Figure 1. XRD patterns of the samples prepared at various tempera-
tures from nickel chloride as the metal source.
J. Nanosci. Nanotechnol. 19, 453–458, 2019
The Synthesis and Use of Nano Nickel Catalysts
(111)
7 nm
from nickel complex
(200) (220)
11 nm
Intensity / a.u.
from nickel hydroxide, no ethanol
13 nm
from nickel hydroxide
15 nm
from nickel chloride
34 nm
the commercial Ni powder
10 20 30 40 50 60 70 80
2θ / º
Figure 2. X-ray diffractograms of the powders obtained from various
metal sources at 50  C.
interaction with the hydrazine reducing agent, several
metal sources were tested (Fig. 2). In all instances, the
preparation of nickel nanoparticles was successful without
any contamination, but with excursive average crystallite
sizes (calculated from the most intense (111) reflection fit-
ting Gaussian curve).
As a reference, commercial metallic nickel powder
was applied and compared to the as-prepared samples.
Although its average grain size is under 50 m written on
the label, XRD measurement was used to determine the
coherently scattering domain, which correlates well with
05crystallite
Dec 2018or20:11:43
subgrain sizes obtained by other charac-
terizing
Publishers
techniques 24
(except when the powder was pre-
Ingenta
by plastic deformation). X-ray line profile analysis
provided with 34 nm value, due to the dislocation bound-
aries and the dipolar walls; however, SEM images indicate
that the particles are in the micron range. By varying the
metal source, the size of the prepared crystallites could be
decreased from 15 nm to 7 nm.
On the X-ray patterns of nanoparticles derived from
Ni(OH)2 , a small, but observable baseline rise was
detected indicating the presence of amorphous nickel
phase. It cannot be residual hydroxide, since oxygen was
not observed by SEM-EDX measurements. Curiously, 4 h
stirring was necessary for all metal source to arrive at
metallic Ni; however, in water, Ni(OH)2 could be trans-
formed to metallic nickel in shorter than 1 h.
3.2. Morphology Characteristics
The SEM micrographs of the nanoparticles prepared in
ethanol show close to spherical Ni aggregates in the
range of 100–300 nm with the narrowest size distribu-
(111)
tion in the images of nickel hydroxide source (Fig. 3).
In the absence of ethanol, aggregation occurred produc-
ing morphology resembling that of nickel hydroxide.25 The
60 70 80
EDX spectrum confirmed the synthesis of metallic nickel,
peaks corresponding to oxygen or chlorine did not turn up
(their appearance would have been the sign of incomplete
transformation). Nevertheless, the transmission electron
455
The Synthesis and Use of Nano Nickel Catalysts Ádám et al.

(A)

(B)

IP: 79.110.19.190 On: Wed, 05 Dec 2018 20:11:43

Copyright: American Scientific Publishers
Delivered by Ingenta
(C)

(D)

Figure 3. SEM images of the as-prepared Ni nanoparticles obtained from A—from nickel chloride, B—from nickel complex, C—nickel hydroxide,
D—nickel hydroxide in the absence of ethanol.

microscope, operating at advanced angular resolution, obtained from the nickel complex verifying that the val-
could provide more detailed picture from the nanoparticles ues of coherently scattering domains determined from the
(Fig. 4). The measurements revealed close fitting square diffractograms were of similar sizes to the nanoparticles
groups with <10 nm diagonals in the images of the powder grown.

456 J. Nanosci. Nanotechnol. 19, 453–458, 2019

Ádám et al. The Synthesis and Use of Nano Nickel Catalysts

(260–340 nm) and a wider (1110–1280 nm). The metal

source was able to dissolve in the reaction medium par-
tially. As a result, hydrazine could react with Ni(OH)2 via
the dissolved Ni2+ . The in situ generated nickel hydroxide
particles were originated from the precipitation reaction
between the nickel cations and the potassium hydroxide
when the nickel complex was the metal source; however,
for the synthesis starting from nickel hydroxide, KOH pel-
lets were not added, and the basic condition was provided
by the dissolution of hydrazine. This interpretation was
confirmed by the unimodal distribution when the starting
metal source was nickel chloride. During the nanoparticle
synthesis, various nickel forms, such as [Ni(C2 H5 OH)6 ]2+ ,
[Ni(N2 H4 m ]2+ , and finally Ni(OH)2 , could be formed in
the order of their kinetic and thermodynamic stabilities.7
Thus, in the larger part of the stirring time, only one form
was present and transformed to nanoparticles.

3.4. Catalytic Test of the Synthesized Nanoparticles

Figure 4. TEM image of nickel nanoparticles from nickel complex as
the metal source.
3.3. Dynamic Light Scattering Investigations
In order to study the degree of the aggregation processes
during nanoparticles synthesis in detail, size distribution
curves were recorded by the dynamic light scattering
IP: 79.110.19.190 On: Wed,ature
method (Fig. 5). Two types of aggregation tendencies
Copyright: were Scientific
American
recognizable: unimodal starting from nickel chloride or bymethoxide
Delivered
hydroxide in ethanol and bimodal for the rest. The latter
indicate two competing routes of nanoparticle formation.
Nickel hydroxide is slightly soluble in water, but insolu-
ble in ethanol, while the solubility of the nickel complex
in ethanol was sufficient to generate nickel-ethanol com-
plex in minute amounts. In this latter instance, aggregation
process followed bimodal distribution, and the aggre-
gates were grown in different size ranges, in a narrower
530
25
1480
20
Frequency / %
The catalytic activities of the nanoparticles and the com-
mercial nickel powder were compared in a Suzuki-
Miyaura cross-coupling reaction producing biaryl, which
has received increased attention by the pharmaceutical
industry as scaffold in the structure of anti-inflammatory,
antihypertensive and antitumor drugs.26 In the reactions,
the work of Park et al.22 was followed with several modi-
fications (the solvent was toluene and the applied temper-
05 Dec
was 2018 20:11:43
decreased to 90  C). Beside pyridine, sodium
Publishers
Ingenta and trimethylamine as stronger bases were also
tested as well as the duration of the synthesis. The obtained
experimental results were similar; formation of polymer-
ized product was detected after 4 h with pyridine, but it
occurred instantly with the stronger bases.
The nickel powder and the nanoparticles from hydrox-
ide obtained from aqueous medium showed similar activi-
ties (Table I), while the yield was the lowest applying the
nanoparticles from ethanolic nickel hydroxide. Curiously,
the nickel particles originating from the complex proved to
be the most efficient catalyst, presumably because of their
smallest crystallite size, thus the increased fraction of edge
sites with enhanced surface energies. Let us mention that
the other nanoparticles did not follow this trend indicating

that other, still unknown parameters are also operational.

15
1110

10 1280 Table I. The Suzuki-Miyaura cross-coupling reaction of

4 -bromoacetophenone and phenylboronic acid yielding a biaryl derivate.
260
5
340
0
100 1000 Catalyst Yield (%)
Diameter / nm Without catalyst 0
from nickel complex Commercial Ni powder 27
from nickel hydroxide, no ethanol
from nickel hydroxide (no water) From nickel hydroxide, no water 12
from nickel chloride From nickel hydroxide, no ethanol 23
From nickel chloride 43
Figure 5. Uni-and bimodal aggregate intensity-weighted size distribu-
From nickel complex 52
tion curves for the nickel nanoparticles.

J. Nanosci. Nanotechnol. 19, 453–458, 2019 457

The Synthesis and Use of Nano Nickel Catalysts
Finally, the catalysts were recovered after the reaction
and their X-ray diffractograms were taken. The calculated
average crystallite sizes and the reflections did not show
significant alterations, and there were no signs of oxide or
other nickel-containing secondary products.
4. CONCLUSIONS
During the synthesis of nickel nanoparticles by the
hydrazine reduction method, it was experienced that the
temperature of the reaction and the quality of the metal
source were crucial in size control, while the application of
ethanol in the synthesis mixture was decisive in the shape
control of the aggregates.
Ni nanoparticles obtained from either metal source
applied were active and recyclable catalysts in the Suzuki-
Miyaura cross-coupling reaction; however, those generated
from the nickel complex exhibited the highest activity. In
addition, the X-ray diffractograms taken after use verified
that the catalysts were not degraded during reaction and it
remained in the metallic state.
Acknowledgment: This work was supported by the
grant GINOP-2.3.2-15-2016-00013. The financial help is
highly appreciated.
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J. Nanosci. Nanotechnol. 19, 453–458, 2019