Influence of silver nitrate concentration on the properties of silver nanoparticles

A. Sobczak-Kupiec1, D. Malina1, Z. Wzorek1, M. Zimowska2

1
Institute of Inorganic Chemistry and Technology, Cracow University of Technology, 24 Warszawska Street, Cracow 31-155,
Poland
2
Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, 8 Niezapominajek Street, Cracow 30-239, Poland
E-mail: dagmaramalina@chemia.pk.edu.pl

Published in Micro & Nano Letters; Received on 25th March 2011; Revised on 8th July 2011

Silver nanoparticles (AgNPs) were prepared by a chemical reduction method in an aqueous solution of silver nitrate and sodium borohydride as
a reducing agent in the presence of polyvinylpyrrolidone as a stabiliser. The effect of silver salt concentration on the synthesis and properties of
AgNPs was investigated. The nanosized silver colloids have been characterised by using scanning electron microscopy and atomic absorption
spectrometry. The optical properties of the silver nanoparticles were studied through UV –vis spectroscopy and Fourier transformed infrared
(FTIR) spectroscopy. Dynamic light scattering measurement using Zetasizer nano ZS was applied for the size estimation of AgNPs. The results
confirmed that silver nanoparticles were formed in each sample independently of silver salt content; however, silver nitrate concentration had a
significant influence on silver nanoparticles morphology and other properties. The absorption intensity, the band of the FTIR spectra intensity
increases with an increase of silver nitrate concentration. Also, the shape and size of particles depends on the silver nitrate concentration.

1. Introduction: In recent years, a great interest in metal nano-
particles properties has been observed. Nanostructured silver particles,
because of their unusual properties, have been the subject of numerous
intensive researches. In comparison with larger particles, they
exhibit new or improved properties (e.g. higher surface to volume
ratio, changes in its total energy, changes in conductivity, different
optical features) [1, 2]. Products based on nanosilver are applied in
the electronic, optic, chemical, textile industries, as well as in phar-
macy, cosmetology, and medicine where they play a significant role
as substrates for synthesis, catalytic materials, sensors or conductors
[3–5]. Silver nanoparticles also demonstrate strong antimicrobial
activity against bacteria, fungi and viruses [6, 7].
A lot of methods have been employed to synthesise silver in nano-
metric sizes. The most widespread and common ones are chemical
reduction methods. The physicochemical methods (e.g. ultrasound,
templates, milling process) and ‘green’ synthesis using microorgan-
isms, enzymes, plants or plant extracts are equally effective, but
sometimes they require complex apparatus. Chemical reduction in
aqueous and non-aqueous solutions is the most common method
for the synthesis of nanoparticles due to its convenience, facility,
being not time-consuming and having a high yield of nanoparticles
produced. Additionally, nanoparticles obtained by chemical route
can be stored for a long time without stability loss [5].
A typical synthesis of silver nanoparticles by chemical reduction
process consists of three main stages. The first one is the reduction
of a silver salt by a reducing agent. AgNO3 is most frequently used
as a source of silver ions. In the second stage, neutral silver atoms
collide with each other, forming stable nuclei and a growth of the
nanoparticle occurs until all metal ions are consumed. The final
stage involves prevention of nanoparticles agglomeration by an
addition of protecting agents. Stabilisers prevent the aggregation
via their interactions with small particles [8, 9].
In the formation of nanostructured silver particles by this method,
morphology (i.e. diameter, size distribution, shape), aggregation
state and stability can be controlled by various parameters. The
initial metal salt concentration, reducing agent/metal salt molar
ratio, stabiliser/metal salt molar ratio or stabiliser concentration
have a significant influence on the morphology and thus the
optical properties of nanoparticles, conductivity, and other charac-
teristics are changed [1, 5, 10, 11]. For example, an increase in
the molar ratio of reducer to metal salt causes a rapid formation
of a large number of nuclei and leads to smaller, monodispersed
metal nanoparticles. In contrast, decreasing the molar ratio
leads to a slow formation of a smaller number of nuclei, and
results in larger nanoparticles with a greater heterogeneity in
size [12].
In the present Letter, we describe an efficient method for silver
nanoparticles synthesis by chemical reduction using silver nitrate
as a silver ions source, sodium borohydride as a reducing agent
and polyvinylpyrrolidone (PVP) as a stabiliser. Moreover, we
have investigated the impact of silver salt concentration on the
optical properties, conductivity and morphology of nanoparticles.
2. Experimental part
2.1. Materials: A synthetic method developed for the purpose of
this experiment enables the production of stable silver nanoparti-
cles, under strictly controlled conditions. The silver nitrate
(.99.9% AgNO3) and sodium borohydride (98% NaBH4) were
purchased from POCh Chemical Company and PVP M.W. 8000
from Acros Organics. All the chemicals were used without further
purification. Doubly distilled water was used for the preparation
of all samples. Sodium borohydride for the reduction of ionic
silver, and PVP to stabilise the silver nanoparticles, were applied.
2.2. Preparation of silver nanoparticles: In the process of silver
nanoparticles preparation by the chemical reduction method, PVP
as an excellent stabiliser and NaBH4 as a reductor have been used
by many researchers. However, there are few reports concerning
the effect of AgNO3 concentrations. A solution of PVP was pre-
pared by dissolving 30 g of PVP in 1000 ml of doubly distilled
water. To make a series of solution I, six different amounts of
AgNO3 were added to 180 ml of the aqueous solution of PVP.
Amounts of sodium borohydrate required for each molar ratio of
AgNO3/NaBH4 ¼ 10/1 were dissolved in 20 ml of PVP solution
to make solution II.
Sodium borohydride solution (solution II) was added dropwise
(about 1 drop/second) to silver nitrate (solution I). The reaction
mixture was stirred vigorously on a magnetic stirrer plate at room
temperature for 15 min, then it was cooled down to 88C. A transpar-
ent solution changes into the characteristic yellow-brown colour,
which indicated the formation of silver nanoparticles.
2.3. Methods: A scanning electron microscopy (SEM) image was
obtained using JEOL JSM 7500F with a back scattered electrons
(BSE) detector. A drop of the sample solution was left to dry on
a copper holder coated with chromium film. UV –vis spectroscopy
measurements (330–700 nm) were performed at room temperature
using a Specord 205 with a 1cm optical length cuvette. Particle size

656 Micro & Nano Letters, 2011, Vol. 6, Iss. 8, pp. 656 –660
& The Institution of Engineering and Technology 2011 doi: 10.1049/mnl.2011.0152
Figure 1 Silver colloids with different concentrations of silver nanoparticles [ppm]
a 100
b 250
c 500
d 750
e 1000
f 2000
distribution was analysed by a dynamic light scattering (DLS)
measurement technique using Zetasizer Nano ZS (Malvern
Instruments, UK). The concentration of silver was determined by
the AAS method with an Analyst 300 Perkin-Elmer spectrometer.
The Fourier transformed infrared (FTIR) investigations were
carried out with the use of a Scimitar Series FTS 2000 Digilab
spectrophotometer in the range of 4000–400 cm21, by the KBr
pellet technique. 16 scans and the resolution of 4 cm21 characterised
these measurements. Electrical conductivity and the pH measure-
ments were determined by an Elmetron CX-741 device equipped
with a conductometer and silver– silver chloride electrode,
respectively.
2.4. Results and discussion: Silver nanoparticles were prepared by
the chemical reduction process, that is, by the reduction of silver
nitrate with sodium borohydrate in the presence of PVP. Thereby,
the silver nanoparticles were colloidally stabilised by the polymer.
As a result, six samples of silver nanoparticles were obtained
with the following concentrations of silver: 100, 250, 500, 750,
1000 and 2000 ppm.
The distinctive colours of silver nanoparticles are due to a phe-
nomenon known as plasmon absorbance. Incident light creates oscil-
lations in conduction electrons on the surface of the nanoparticles
and electromagnetic radiation is absorbed [13]. A general obser-
vation was that upon synthesis at different concentrations, the
colour of samples gradually changed from yellow through to dark
brown to a dark greenish colour (Fig. 1). All the samples were trans-
parent and became darker with increasing silver concentrations.
The silver nanoparticles were characterised by UV –vis spec-
troscopy. This technique appeared to be very useful in the analysis
of nanoparticles [14 –16]. As illustrated in Fig. 2, a strong, broad
and asymmetric peak located between 411 and 438 nm was
observed for the silver nanoparticles prepared using PVP and
Figure 2 UV –vis absorption spectra of silver nanoparticles obtained at
different silver concentrations [ppm]
a 100
b 250
c 500
d 750
e 1000
f 2000
Micro & Nano Letters, 2011, Vol. 6, Iss. 8, pp. 656 –660
doi: 10.1049/mnl.2011.0152
NaBH4 with different silver concentrations. The observation of
this peak, assigned to a surface plasmon, is well-documented for
various metal nanoparticles with sizes ranging from 2 to 100 nm
[14 –16].
The primary study shows that the absorption intensity increases
when the concentration of AgNO3 increases, which reflects in the
formation of more Ag nanoparticles. At a low concentration of
AgNO3 , the maximum absorption wavelength gives rise to a blue
shift, meaning a decrease in the particles size. At a high concen-
tration of AgNO3 , the maximum absorption gives rise to a red
shift, meaning that the particles’ size increased [17, 18] and the
large silver aggregates were formed. Concentration of silver in
all samples, determined by the atomic absorption spectrometry
(AAS) was lower than the theoretical (calculated) value.
The results shown in Table 1 indicate that the conductivity of
silver nanoparticles suspension increased with a growing amount
of silver nitrate and sodium borohydrate. The conductivity of
PVP solution amounted to 0.329 mS. An increase in the conduc-
tivity from 0.410 to 2.370 mS in nanoparticles samples was due
to the presence of the ions that resulted from sodium nitrate dis-
sociation in water solution. The amount of sodium nitrate increased
with the increasing quantities of related substrates. A reaction
between silver nitrate and sodium borohydrate in a water solution
could be described by the following equations [19]
1 1
AgNO3 + NaBH4  Ag + H2 + B2 H6 + NaNO3 (1)
2 2
B2 H6 + H2 O  6H2 + 2H3 BO3 (2)
NaBH4 + 2H2 O  NaBO2 + 4H2 (3)
BH4− + H3 O+ + 2H2 O  H3 BO3 + 4H2 (4)
Besides the reaction (1), simultaneous (3, 4) and coupled (2)
reactions could proceed in a water environment [20]. A decrease
in pH value that resulted from the formation of boric acid could
also be the cause for an increase in the conductivity of the investi-
gated suspensions (Table 1). According to Song et al. [8], metal
reduction generally proceeds according to the following reaction
Ag+ + BH4 − + 3H2 O  Ag + B(OH)3 + 3.5H2 (5)
Taking into consideration reaction (1) proposed by Bruzzoniti et al.
[19], one product (diborane) is absent in (5).
Fig. 3 shows the electron microscopy and corresponding size
distribution of the silver nanoparticles obtained from the reduction
of silver nitrate by sodium borohydrate. The radius of silver nano-
particles increased when the silver concentration was in the range
of 100–500 ppm. It was found that a mean particle radius decreased
significantly with an increasing silver nitrate concentration when the
silver concentration was within 500– 2000 ppm, which means that
with an increasing AgNO3 concentration the nucleation rate of
the silver particles reached an optimal level. When the silver con-
centration is higher than 3000 ppm, the silver colloid is unstable
and easy to flocculate and thus the SEM microphotograph has not
been presented. Fig. 3a indicates that there are few small silver
657
& The Institution of Engineering and Technology 2011
Table 1 Ag concentration, l max, pH and conductivity measurement results of nanosilver suspensions

Ag theoretical concentration [ppm] Unit PVP 100 250 500 750 1000 2000

Ag concentration (AAS method) [ppm] – 90.7 206.5 436.2 674.5 844.8 1896.8
l max [nm] – 406.0 411.0 412.0 422.0 426.0 438.0
pH – 7.22 4.29 4.29 4.14 3.49 3.46 3.32
Conductivity [mS] 0.329 0.410 0.553 0.756 0.954 1.256 2.370

Figure 3 BSE–SEM images and size distribution of silver suspension obtained at different silver concentrations [ppm]
a and b 100
c and d 250
e and f 500
g and h 750
i and j 1000
k and l 2000

nanoparticles generated in the synthesis with silver nitrate (Ag con-
centration 100 ppm).
The nanoparticles obtained at silver concentrations of 250 and
500 ppm were more prone to agglomeration (Figs. 3c and e) than
in the remaining suspensions. However, a considerable amount of
large particles was obtained at lower silver concentrations
(Figs. 3d and f ). The considerable share in particles of the shape
of a prism with a hexagonal base was observed at 750 (Fig. 3g),
1000 (Fig. 3i) and 2000 ppm (Fig. 3k). On the contrary, there
were more but smaller nanoparticles, which means that in the
higher silver nitrate concentration, a faster nucleation of the silver
particles was observed. Therefore large numbers of particles with
a relatively small diameter were formed. When silver nanoparticles
are synthesised in a high AgNO3 concentration, a rapid reduction
process takes place to form a larger number of nuclei. As a result,
small nanoparticles with a high specific surface area are formed
in a short time. On the other hand, there are a large number of
silver atoms available for the growth of the nucleated particles to
form larger nanoparticles. In addition, the collision frequency of
the formed particles increases significantly with a silver nitrate
concentration. Thus, the particles are easy to aggregate into larger
ones at high silver nitrate concentration.
The FTIR spectra of PVP and suspension containing silver nano-
particles and PVP are presented in Fig. 4. The main feature of all
of the spectra was a strong band at 1680–1674 cm21, which corre-
sponded to amide carbonyl of PVP. According to the literature
[21, 22], the shape of the amide carbonyl stretch absorption is one
of the broadest of the carbonyl family and was positioned between
1695 and 1615 cm21. Other bands in all of the spectra were centred
at 1466 and 1427 cm21, which resulted from the vibration of the ter-
tiary nitrogen. The FTIR spectra showed the presence of a band at
1547–1542 cm21 and it was identified as amide II and arose due
to carbonyl stretch and –N–H stretch vibrations in the amide linkages
of PVP. The band at 2953 cm21 is attributed to the asymmetric C–H
stretching vibration of CH3 and the band at 2874 cm21 is assigned to
the symmetric C–H stretching vibration of CH2 .

658 Micro & Nano Letters, 2011, Vol. 6, Iss. 8, pp. 656 –660
& The Institution of Engineering and Technology 2011 doi: 10.1049/mnl.2011.0152
Figure 4 FTIR spectra in the region 4000– 500 cm21 of the following samples
a PVP
b 100 ppm
c 250 ppm
d 500 ppm
e 750 ppm
f 1000 ppm
g 2000 ppm
The FTIR spectra of the silver particles suspensions were similar
to that of the PVP. However, the slightly visible differentiating
shifts in the spectra of pure PVP and silver colloids suggest coord-
ination between silver nanoparticles and the stabiliser. A shift of the
carbonyl absorption band to lower frequencies from 1547 (Fig. 4a)
to 1541 cm21 (Figs. 4a –g) was observed. For this band displace-
ment could be responsible for coordination of the amide carbonyl
oxygen with silver particles. In the FTIR spectra of silver nanopar-
ticles (Figs. 4b–g), the band at 1387 cm21 appeared and its intens-
ity increased with increasing concentrations of silver nitrate used for
the synthesis. According to [21], the presence of the band at
1387 cm21 indicates the presence of silver nitrate in the PVP
matrix.
3. Conclusions: The present work reveals a simple, cost-effective
wet chemical synthetic route to form nanosilver suspensions. In
spite of the fact that the chemical reduction process needs an ex-
perimentally selected reaction condition, the synthesis of metallic
nanoparticles is fast, it does not require any complex apparatus
and it allows producing large quantities of nanoparticles in a
short period of time under mild reaction conditions.
The six suspensions resulting from different initial concentrations
of silver nitrate exhibit significant absorbance in the visible region,
and the corresponding spectra show a broad and well-defined
band that peaks at 406 –438 nm. The position of an absorption
band depends on the silver nitrate concentration. In general, as
the particles become larger the plasmon peak shifts to longer
wavelengths and broadens. However, with an increasing AgNO3
concentration, the nucleation rate of the silver particles reached to
optimal level. It was also observed that silver nanoparticles
were easy to aggregate into larger particles, owing to the rise of
the collision frequency with an increasing of silver salt content.
The FTIR investigations of the silver particles suspensions
confirmed that there were slightly observable differentiating shifts
in spectra of pure PVP and silver colloids suggesting the coord-
ination between the silver nanoparticles and the stabiliser.
As mentioned above, the products based on AgNPs are currently
applied in different industries. However, the nanoproducts obtained
by our research team will be used as structure modifiers of the
Micro & Nano Letters, 2011, Vol. 6, Iss. 8, pp. 656 –660
doi: 10.1049/mnl.2011.0152
polymer composites, as well as additives improving the properties
of selected biomaterials.
4. Acknowledgment: The research was supported by The National
Centre for Science in Poland.
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