Materials Chemistry and Physics 114 (2009) 530–532

Contents lists available at ScienceDirect

Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Materials science communication

Microwave-assisted synthesis of silver nanoparticles using ethanol as

a reducing agent
Angshuman Pal, Sunil Shah, Surekha Devi ∗
Department of Chemistry, Faculty of Science, The Maharaja Sayajirao University of Baroda, Vadodara 390002, Gujarat, India

a r t i c l e i n f o a b s t r a c t

Article history: Silver nanoparticles were prepared by microwave irradiation of silver nitrate (AgNO3 ) solution in ethanolic
Received 3 September 2008 medium using polyvinylpyrrolidone (PVP) as a stabilizing agent. Ethanol was observed to act as a reduc-
Received in revised form 11 November 2008 ing agent in the presence of microwave. Appearance of surface plasmon band at 416 nm indicated the
Accepted 17 November 2008
formation of silver nanoparticles. Highly monodispersed stable polycrystalline silver nanoparticles were
obtained within 5 s of microwave irradiation. Through transmission electron microscopy silver nanopar-
Keywords:
ticles were observed to be spherical with 10 ± 5 nm diameter. Silver nanoparticles exhibited fluorescence
Nanostructures
band at 491 nm.
Electron microscopy
© 2008 Elsevier B.V. All rights reserved.
Optical properties

1. Introduction by molecular friction. The MW power dissipation per unit volume

in a material (P) is given by Eq. (1)
Nanosize metal particles have attracted significant attention
because of their unusual size-dependent optical and electronic P = cE 2 fε = cE 2 fε tan ı (1)
properties. Among the metals, silver nanoparticles show potential
applications in various fields such as the environment, bio-
where c is a velocity of radiation, E is an electric field in the mate-
medicinal, catalysis, optics and electronics [1]. In particular, Ag
rial, f is frequency of radiation, and ε and ε are the dielectric
nanoparticles are used in diagnostic biomedical optical imaging
and dielectric loss constants, respectively. ε represents the rela-
[2]. The surface plasmon resonance and large effective scattering
tive permittivity, which is a measure of the ability of a molecule
cross-section of individual silver nanoparticles make them ideal
to be polarized by an electric field and tan ı = ε /ε is the energy
candidates for molecular labelling, where phenomenon such as sur-
dissipation factor or loss tangent. In the above equation ε is most
face enhanced Raman scattering can be exploited [3]. Since the
important physical parameter that describes the ability of a mate-
anisotropic nanoparticles have greater surface area than spheri-
rial to heat in the MW field. Water and alcohols have high dielectric
cal nanoparticles, their metal enhanced fluorescence is higher than
losses and a high reducing ability. Therefore they are the ideal sol-
that of spherical nanoparticles [4]. Silver nanoparticles can be syn-
vents for microwave heating. The boiling point of ethanol is 78 ◦ C
thesized using various methods such as chemical reduction [5],
and ε and ε values are 6.08 and 24.3 respectively. Wang et al. [14]
electrochemical [6], ␥-radiation [7], laser ablation [8], photochem-
have synthesized shorter than 50 nm Ag nanoparticles by dissolv-
ical [9], sonochemical [10] and sputtering [11]. Among these the
ing PVP, glucose and sodium hydroxide in water at 60 ◦ C through
most popular method for preparation of silver colloid is chemi-
thermal heating. Gao et al. [15] have reported the synthesis of sil-
cal reduction of silver salt in the presence of any stabilizing agent.
ver nanoparticles by PVP-assisted N,N-dimethylformamide (DMF)
Most commonly used stabilizing agents are polymers [12] and sur-
reduction at 140 ◦ C for 3 h. They could get Ag decahedrons with edge
factants [13]. Recently for the preparation of silver nanoparticles,
size 80 nm. Tusji and co-workers [16] have reviewed the prepara-
microwave heating (MW) has been reported to have better promise
tion of Ag nanostructures in PVP using microwave.
over thermal heating. In the microwave frequency range 300 MHz
Polymer–metal nanoparticle composites seem to receive spe-
to 300 GHz, polar molecules such as H2 O try to orient with the elec-
cial attention because of their application potential in sensors
tric field. When the dipolar molecules try to re-orient with respect
[17], actuators [18], electrodes for fuel cells [19], optical and opto-
to an alternating electric field, they lose energy in the form of heat
electronic devices [20]. Silver nanoparticles have characteristic
fluorescence emission property [21]. Zheng et al. [22] observed fluo-
rescence emission for dendrimer-encapsulated silver nanodots. For
∗ Corresponding author. Tel.: +91 2652795552. all the above applications, especially for sensors and optical devices
E-mail address: surekha devi@yahoo.com (S. Devi). highly monodispersed particles are required.

0254-0584/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2008.11.056
 A. Pal et al. / Materials Chemistry and Physics 114 (2009) 530–532 531

Here in this paper we are describing the preparation of spher-

ical, monodispersed, PVP stabilize silver nanoparticles under MW
heating using ethanol as a reducing agent.

2. Experimental

2.1. Materials

All chemicals and materials were used as received: AgNO3 and polyvinylpyrroli-
done (PVP) (Mw = 10,000) were purchased from Sigma–Aldrich, UK and ethanol from
Fluka.

2.2. Preparation of PVP-silver nanoparticle composites

For the synthesis of Ag nanoparticles SHARP make microwave oven (model: R-

259) was used. In a typical procedure, 10 ml of 1% (w/v) ethanolic solution of PVP
and 0.2 ml of 0.1 M AgNO3 were taken in a 25 ml closed conical flask and placed
in a microwave oven that was operated at the 100% power of 800 W and frequency
2450 MHz for 5 s. The colourless solution instantaneously turned to the characteristic
pale yellow colour, indicating the formation of silver nanoparticles. The advantage
of microwave-mediated synthesis over the conventional heating is the improved
kinetics of the reaction generally by one or two order of magnitude, due to rapid
initial heating and the generation of localized high-temperature zones at reaction
sites [23].

2.3. Characterization
Characteristic optical properties of Ag nanoparticles were recorded using
PerkinElmer Lambda 35 UV–vis spectrophotometer. Spectra were recorded using
1 cm3 quartz cell. Emission spectrum of the solution was recorded by using
spectrofluorometer from JASCO. Size, shape and particle size distributions were
determined using a JEOL JEM-2011 transmission electron microscope operated at
an accelerating voltage of 200 kV. Images were recorded using a Gatan DualVision
600t CCD camera attached to the microscope and were analyzed using Gatan Digital
Micrograph Version 3.11.1. The TEM was calibrated for diffraction and imaging mode
using standard samples. The resolution of the system was calibrated with manganese
(Mn). Samples were prepared for TEM analysis by placing a drop of the solution on
a carbon coated copper grid and drying in air. The energy dispersive X-ray analysis
was undertaken with a Princeton Gamma Tech Prism 1G system with a 10 mm2 sil-
icon detector attached to the TEM and the peaks were analysed with Imix 10.594
software.
3. Results and discussion
A typical TEM image of the Ag nanoparticles in Fig. 1 shows
the spherical particles of 10 ± 5 nm diameter. The particles were
observed to be highly monodispersed and uniformly distributed. As
Fig. 1. TEM image of the silver nanoparticles. Inset shows the digital photograph of
PVP stabilized silver nanoparticles in ethanol medium.
the TEM analysis was carried out on 100 times dilution of colloidal
suspension only few particles were observed in the small section
of high-resolution image. Use of microwave irradiation in the syn-
thesis is showing promise not only due to faster heating but it also
gives internal uniform heating resulting into uniformly distributed
monodispersed particles. The formation of silver nanoparticles was
confirmed by change in colour of the solution. The colourless silver
nitrate solution turns yellow within 5 s of microwave irradiation.
Inset in Fig. 1 shows the digital photograph of Ag nanoparticles in
PVP ethanol solution. The visible spectrum (Fig. 2) of silver nanopar-
ticles shows the characteristic surface plasmon band at 416 nm that
is slightly higher than our previous report [5,13]. The surface plas-
mon band not only depends on the particle size but also on the
refractive index of the surrounding medium and that is the reason
for slightly red shift on surface plasmon resonance peak for these
silver nanoparticles. To examine the fluorescence property of these

Fig. 2. UV–vis and fluorescence spectroscopy of silver nanoparticles.

532 A. Pal et al. / Materials Chemistry and Physics 114 (2009) 530–532
Fig. 3. High-resolution TEM image of silver nanoparticles.
Fig. 4. Energy dispersive X-ray for silver nanoparticles.
particles the solution was excited at 416 nm and emission of flu-
orescence was observed at 491 nm (Fig. 2). For Ag nanoparticles
stabilized by [poly(styrene)]-dibenzo-18-crown-6-[poly(styrene)]
in solutions Gao et al. [24] have reported emission band at 486 nm
upon excitation at 408 nm. The origin of the fluorescence can
be attributed to the promotion of d band electrons of the silver
metal nanoparticles on absorption of the incident photon energy,
to higher electronic states in the sp-band. The high-resolution TEM
image of these silver nanoparticles (Fig. 3) reveals crystalline char-
acter and ordered orientations of the lattice fringes. The energy
dispersive X-ray spectroscopy (EDX) (Fig. 4) confirms the forma-
tion of silver particles. The EDX spectrum was taken from a random
assembly of Ag nanoparticles. The signal of Cu originated from the
carbon coated Cu grid.
4. Conclusions
Spherical, monodispersed silver nanoparticles were synthesizes
under microwave oven by using PVP as a stabilizing agent and
ethanol as reducing agent. This rapid synthesis technique can be
a promising method for the preparation of highly monodispersed
spherical silver nanoparticles and that can be applicable to the other
noble metals also.
Acknowledgements
The authors are thankful to GUJCOST (Gadhinagar, Gujarat) for
the financial support.
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