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Electrochemical method for the synthesis of silver nanoparticles

Article in Journal of Nanoparticle Research · July 2009

DOI: 10.1007/s11051-008-9513-x

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J Nanopart Res (2009) 11:1193–1200
DOI 10.1007/s11051-008-9513-x

RESEARCH PAPER

Electrochemical method for the synthesis of silver

nanoparticles
Rashid A. Khaydarov Æ Renat R. Khaydarov Æ
Olga Gapurova Æ Yuri Estrin Æ Thomas Scheper

Received: 31 March 2008 / Accepted: 3 September 2008 / Published online: 21 September 2008
Ó Springer Science+Business Media B.V. 2008

Abstract The article deals with a novel electro- under ambient conditions. Silver crystal growth on
chemical method of preparing long-lived silver the surface of the cathode in the electrochemical
nanoparticles suspended in aqueous solution as well process used was shown to result in micron-sized
as silver powders. The method does not involve the structures consisting of agglomerated silver nanopar-
use of any chemical stabilising agents. The morpho- ticles with the sizes below 40 nm.
logy of the silver nanoparticles obtained was studied
using transmission electron microscopy, scanning Keywords Silver
Nanoparticle
PVP

electron microscopy, atomic force microscopy and Electrochemical synthesis
Colloids
dynamic light scattering measurements. Silver nano-
particles suspended in water solution that were
produced by the present technique are nearly spher-
ical and their size distribution lies in the range of 2 to Introduction
20 nm, the average size being about 7 nm. Silver
nanoparticles synthesised by the proposed method The last decade has seen the development of a hoist
were sufficiently stable for more than 7 years even of different methods for the synthesis and charac-
terization of metal nanoparticles and powders
thereof (Feldheim and Foss 2002). Owing to their
properties being distinctly different from those of
R. A. Khaydarov
R. R. Khaydarov (&)
O. Gapurova the bulk metal, nanoparticles are finding their way
Institute of Nuclear Physics, Uzbekistan Academy into various areas of science and technology
of Sciences, Tashkent, Uzbekistan
(Mazzola 2003; Anselmann 2001; Bönnemann and
e-mail: [email protected]
Richards 2001; Biswas and Wu 2005). In particular,
Y. Estrin nanoparticles of silver have attracted much attention
ARC Centre of Excellence for Design in Light Metals, because of a broad range of their possible applica-
Department of Materials Engineering, Monash University
tions including medicine (Salata 2004), catalysis
and CSIRO Division of Materials Science and
Engineering, Clayton, VIC, Australia (Lewis 1993), textile engineering (Lee and Jeong
e-mail: [email protected] 2005), biotechnology and bioengineering (Niemeyer
2001), water treatment (Solov’ev et al. 2007), elec-
T. Scheper
tronics (Li et al. 2005) and optics (Murphy et al.
Institute of Technical Chemistry, Leibniz University,
Hannover, Germany 2005). Many approaches were developed to obtain
e-mail: [email protected] silver nanoparticles of various shapes and sizes,

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1194 J Nanopart Res (2009) 11:1193–1200

including laser ablation (Lee et al. 2001), gamma Materials and methods
irradiation (Long et al. 2007), electron irradiation
(Bogle et al. 2006), chemical reduction by inorganic The proposed process for obtaining silver nanoparti-
and organic reducing agents (Bönnemann and cles is based on the use of an inexpensive two-
Richards 2001), photochemical method (Mallick electrode setup in which the anode and the cathode
et al. 2004), microwave processing (Yin et al. are made from the bulk Ag metal to be transformed
2004), and thermal decomposition of silver oxalate into Ag colloidal particles. We employed two
in water and in ethylene glycol (Navaladian et al. polished silver plates (85 mm 9 20 mm 9 4 mm)
2007). Reetz and Helbig (1994) were the first to as the anode and the cathode, being vertically placed
describe in detail an electrochemical technique for face-to-face 10 mm apart. The electrodes were
the synthesis of nanoparticles, in which a metal immersed in an electrochemical cell filled with
sheet was anodically dissolved and the intermediate 500 mL of distilled water obtained from an ordinary
metal salt formed was reduced at the cathode, giving commercially available water distiller (DE-25,
rise to metallic particles stabilised by tetraalkylam- Russia). Electrolysis was performed in the tempera-
monium salts. This work was successfully adopted ture range 20–95 °C at a constant voltage of 20 V.
for the electrochemical synthesis of the silver Additional technological keys to the electrochemical
nanoparticles in acetonitrile containing tetrabutyl- synthesis of silver nanoparticles lie in changing the
ammonium salts by Rodrı́guez-Sánchez et al. polarity of the direct current between the electrodes
(2000). Using a similar approach, silver nanoparti- every 30–300 s, and intensive stirring during the
cles were obtained by potentiostatic or galvanostatic process of electrolysis to inhibit the formation of
polarisation of silver in ethanol solution by precipitates. The silver nanoparticle solutions pro-
Starowicz et al. 2006). In the work of Yin et al. duced in this way were stored under ambient
(2003), Poly(N-vinyl-2-pyrrolidone) (PVP) was conditions in glass containers.
essential in the process of electrochemical synthesis The concentration of the silver nanoparticles in
of silver particles. The main advantages of the solutions was determined by neutron activation
electrochemical methods lie in the high purity of analysis (Soete et al. 1972). The samples were
particles and the possibility of the nanoparticle size irradiated in the nuclear reactor of the Institute of
control by adjusting the current density without a Nuclear Physics (Tashkent, Uzbekistan). The product
need for expensive equipment or vacuum. The key of the nuclear reaction 109Ag(n,c)110mAg has the half-
to the success of electrochemical methods is the life T1/2 = 253 days. The silver concentration was
right choice of the chemical agents and the process determined from the measurements of the intensity of
conditions. However, as pointed out earlier (Rodrı́guez- gamma radiation with the energy of 0.657 MeV and
Sánchez et al. 2000), the method has its limitations, 0.884 MeV emitted by 110mAg. A Ge(Li) detector
as the deposition of silver on the cathode during the with a resolution of about 1.9 keV at 1.33 MeV and a
electrochemical process diminishes the effective 6144-channel analyser were used for recording
surface available for particle production. As the gamma-ray quanta.
entire cathode surface gets covered with the silver Dynamic light scattering (DLS) measure-
electrodeposits, the particle production comes to a ments were carried out at 25 °C using a Zetasizer
halt altogether. (ZEN3600, Malvern Instruments, UK) to estimate the
An important issue in the current search for size distribution of silver nanoparticles in solutions.
simpler and cost-effective methods for the synthesis The morphology of silver powder deposited on the
of nanoparticles is finding ways to avoid the use of surface of the cathode during the electrochemical
stabilising agents in the electrochemical processes process was observed by field emission scanning
involved. In this article, we present a novel electro- electron microscopy (FE-SEM; JSM-6700F, JEOL,
chemical method for preparing long-lived silver Japan). The size and shape of the nanoparticles in
nanoparticles suspended in aqueous solutions as solution were determined by transmission electron
well as silver powders deposited on the electrodes, microscopy (TEM) (LEO-912-OMEGA, Carl Zeiss,
which does not involve any chemical stabilising Germany). Energy dispersive X-ray spectrometer
agents. (EDS) attached to the TEM was used to determine

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J Nanopart Res (2009) 11:1193–1200 1195

the chemical composition of the samples. The size Ag0  e ! Agþ1

values were averaged over more than 150 nanopar-
ticles from different TEM micrographs of the same 2. Release of the oxygen gas:
sample.
The silver nanoparticles suspended in aqueous 2H2 O  4e ! O2 " þ 4Hþ
solutions were also imaged by atomic force micros- due to the electrolysis of water, with simultaneous
copy (AFM) (Solver P47Bio, NT-MDT Co., Russia) Ag2O film deposition on the surface of the anode;
in contact mode using freshly cleaved mica surfaces
as substrates. 3. Ag? ions migration to the cathode;
4. Reductive formation of zero-valent Ag atoms on
the cathode:
Results and discussion
Agþ1 þ e ! Ag0
As distinct from most non-electrochemical methods and release of the hydrogen gas:
(Lee et al. 2001; Long et al. 2007; Bogle et al. 2006; 2H2 O þ 2e ! H2 " þ2OH
Mallick et al. 2004; Yin et al. 2004; Navaladian et al.
2007), the proposed approach of electrochemical 5. Formation of silver nanoparticles via nucleation
synthesis does not require the use of vacuum and growth due to attractive van der Waals forces
chambers, sophisticated preparation or expensive between Ag atoms;
equipment. The process of synthesis proposed here 6. Separation of synthesised silver nanoparticles
involves three major stages, which are described from the cathode and their further migration
below. caused by vigorous stirring of the solution.

Stage I: formation of a colloidal solution of silver Upon application of a voltage, the reactions
nanoparticles described above set in and the electrical current
continuously increased until it reached a saturation
This stage comprises the following steps (Fig. 1): level. The warmer was the water, the faster was the
reaction and the higher was the value of the saturation
1. Oxidative dissolution of the sacrificial Ag anode: current (cf Fig. 2).
In the described first stage of the electrochemical
synthesis, the polarity of the direct current between
the electrodes was periodically changed, which
significantly reduced the electrodeposition of silver
on the cathode. As soon as the polarity changes,
Ag2O on the surface of the former cathode starts
reducing in a reaction with hydrogen

80
70
60
50
I, mA

40
30
20
10
0
0 20 40 60 80 100 120
t, min
353 K 338 K 328 K 319 K 313 K
Fig. 1 Electrochemical formation of silver nanoparticles in
distilled water Fig. 2 Current versus process time for different temperatures

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1196 J Nanopart Res (2009) 11:1193–1200

Ag2 O þ H2 ! 2Ag þ H2 O individual trial resulted in a larger average size and a

higher concentration of silver nanoparticles. In order
at temperatures above 50 °C. We varied the period of
to obtain stable silver nanoparticles with a concentra-
the polarity changes in the range of 30 to 300 s. It
tion in the range of 20 to 40 mg/L, it was necessary to
was found empirically that 4 min was an optimum
ensure a reaction time of 50–70 min in the temperature
period. At smaller values, agglomeration of particles
range of 50 to 80 °C.
in the solution was enhanced at the cost of silver film
deposition at the cathode. For values of the period
exceeding 4 min, a gradual decrease of the effective Stage II: filtration
surface for the particle production occurred, owing to
a significant growth of silver electrodeposition on the As was shown by DLS and TEM measurements, a
cathode. By periodically changing the polarity every typical sample of silver nanoparticles solution con-
4 min, the film deposition at the electrodes was tains a small amount of large Ag colloids after the
reduced as compared to known electrochemical first stage as well (see Fig. 3). In order to remove
methods (Reetz and Helbig 1994; Rodrı́guez-Sánchez these larger colloids and to provide reduction of the
et al. 2000; Starowicz et al. 2006), and the produc- silver ions present in the solution, we propose to
tion of nanoparticles was enhanced resulting in larger implement a filtration stage. Passing the colloidal
concentrations of silver colloids. solution through a paper filter, narrows the range of
The solutions were tested for sizes of suspended size distributions of the synthesised silver nanopar-
silver nanoparticles as soon as current saturation was ticles (see Fig. 4) and also provides additional
reached. TEM and DLS studies demonstrated that the reduction of Ag ions:
average size of silver nanoparticles in the colloidal
Agþ1 þ e ! Ag0
solution decreases with increase in the current density,
as was shown in (Reetz and Helbig 1994) theoretically. As a result, the ratio c(Ag?)/c(Ag) decreases, where
The rate of the reaction was shown to increase with c(Ag?) is the concentration of silver ions and c(Ag) is
decrease in the distance between the electrodes and the concentration of silver nanoparticles suspended in
increase in the voltage. A longer reaction time for each the solution, respectively.

Fig. 3 Typical DLS-images of size distribution by intensity (left) and number (right) of silver nanoparticles obtained after Stage I

Fig. 4 Typical TEM image

and size distribution of
silver nanoparticles
obtained after Stage II

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J Nanopart Res (2009) 11:1193–1200 1197

Stage III: additional treatment In our studies, as a variant of the processing, PVP
was also used as a protective medium for the silver
A third stage of Ag nanoparticle synthesis involves colloids. PVP is known to affect the molecular
the additional treatment of the smallest-size fraction motion of reduced silver, inhibiting the aggregation
of silver nanoparticles remaining in solution after the of nanoparticles (Yin et al. 2004). Sustainability of
filtering stage. It consists in adding hydrogen peroxide the solution of nanoparticles after Stage II (‘Sample
to a level of up to 0.005% concentration of H2O2 to A’) and Stage III (‘Sample B’) of the proposed
the solution. Due to the reaction synthesis was monitored over 300 days and com-
pared with that of the samples containing PVP
Ag2 O þ H2 O2 ! 2Ag þ H2 O þ O2 ;
(‘Sample A ? PVP’ and ‘Sample B ? PVP’). PVP
silver oxide is reduced to Ag which is released in the was added to the samples in such a way as to produce
solution. Due to this process, the size of the silver a mass relation of Ag colloids and PVP of 1:20. As
nanoparticles is reduced while new Ag nanoparticles one can see from Table 1, the nanoparticles prepared
may be forming as well. The details of this process, can be stored for months under ambient conditions
whose outcome consists in a significant refinement of with only little coarsening; small additions of PVP to
the nanoparticle size, are not fully understood as yet. electrochemically synthesised silver nanoparticle
Examination of TEM images taken 2 weeks after the solutions act to enhance their stability.
addition of H2O2 revealed that silver nanoparticles DLS and TEM measurements showed that an
suspended in water solution were nearly spherical and increase in the PVP concentration enhances the
that their size distribution fell in the range of 2 to stability of colloids. On the other hand, it leads to
20 nm, the average size being about 7 nm (cf. Fig. 5). more viscous colloidal solution potentially compli-
EDS analysis of silver nanoparticles (cf. Fig. 6) cating the process of impregnating different materials
has shown a presence of Ag2O in the solution after with silver nanoparticles. This effect may be relevant
Stage II and an efficiency of reduction of silver for paints modified with silver nanoparticles, textile
oxides in the solution during Stage III. fabrics (Jeong et al. 2005; Lee and Jeong 2004) etc.,

Fig. 5 Typical TEM image

and size distribution of
silver nanoparticles
obtained after Stage III

Fig. 6 EDS analysis after

stages II (left) and III
(right). Carbon and copper
peaks are from the carbon-
coated copper sample grid

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1198 J Nanopart Res (2009) 11:1193–1200

Table 1 Mean size of silver nanoparticles from different One of the main advantages of the proposed
colloidal solution samples electrochemical method is a high degree of stability
Days Mean diameter (nm) of the synthesised silver nanoparticles. As demon-
strated by AFM measurements (see Fig. 7), a sample
Sample Sample Sample Sample
A A ? PVP B B ? PVP solution of silver nanoparticles obtained by the
proposed method in a process involving stages I
1 24 ± 12 24 ± 12 7±3 7±3 and II remained stable over 7 years of storage under
10 26 ± 12 24 ± 12 9±4 8±4 ambient conditions. On average, only moderate
20 31 ± 15 26 ± 12 10 ± 4 9±4 growth of the particles was found, although coarse
100 40 ± 17 28 ± 13 13 ± 5 11 ± 4 particles with the diameter of up to 100–150 nm
300 47 ± 20 31 ± 14 19 ± 7 13 ± 5 occurred occasionally (cf. Fig. 7). Moreover X-Ray
spectrum of the sample obtained by EDS is analogous
to that shown in Fig. 6 (right), proving the purity of
silver nanoparticles.
A ‘by-product’ of the silver nanoparticle produc-
tion by electrolysis is the re-deposition of silver on
the cathode. The morphology of the deposit was also
studied in this work. Due to its weak adhesion to the
substrate, it could be easily removed mechanically in
the form of grey coloured powder consisting of rather
large (*1 lm) polyhedron-shaped particles and
micron-sized platelets (Fig. 8). These consisted of
agglomerated silver nanoparticles with sizes up to
40 nm, cf. Fig. 9.

Conclusions

Silver nanoparticles obtained in a three-stage process

based on the electroreduction of anodically solved
Fig. 7 AFM image of silver nanoparticles obtained by the silver ions in water have been studied. Various
electrochemical method and stored for 7 years. (Substrate: technological keys to improve the output by varying
freshly cleaved mica.)
the process conditions have been considered. The
morphology of the colloidal silver nanoparticles and
and it needs to be considered in the light of potential the powders deposited on the electrodes was studied
industrial applications of the synthesised silver using DLS, TEM and SEM measurements. These
nanoparticles. studies have shown that silver nanoparticles

Fig. 8 Typical SEM-

images of polyhedron-
shaped silver powders (left)
and platelets (right). Note
the scale bars of 1 and
10 lm, respectively

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J Nanopart Res (2009) 11:1193–1200 1199

include Stage III, the average nanoparticle size of

about 20 nm or 7 nm, respectively, can be achieved.

Acknowledgements RR Khaydarov acknowledges partial

support of this work through the INTAS Fellowship Grant
No. 5973 for Young Scientists under the ‘Uzbekistan—INTAS
2006’ program.

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