Spectrochimica Acta Part A 75 (2010) 1078–1081

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Honey mediated green synthesis of silver nanoparticles

Daizy Philip ∗
Department of Physics, Mar Ivanios College, Nalanchira, Thiruvananthapuram 695015, Kerala, India

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

Article history: The paper reports the pH controlled synthesis of silver nanoparticles using honey as reducing and stabiliz-
Received 19 September 2009 ing agents. By adjusting the pH of the aqueous solution containing metal ions and honey, nanoparticles of
Accepted 17 December 2009 various size could be obtained at room temperature. The nanoparticles were characterized by UV–visible,
high-resolution TEM, XRD and FTIR measurements. The colloid obtained at a pH of 8.5 is found to consist of
Keywords: monodispersed and nearly spherical silver nanoparticles of size ∼4 nm which is a significant advancement
Nanostructures
in biosynthesis. The high crystallinity with fcc phase is evidenced by clear lattice fringes in the high-
Silver nanoparticles
resolution TEM image and peaks in the XRD pattern corresponding to (1 1 1), (2 0 0), (2 2 0), (3 1 1) and
Surface plasmon resonance
UV–visible spectra
(2 2 2) planes. FTIR spectrum indicates that the nanoparticles are bound to protein through the carboxylate
ion group.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction Natural honey – the food of Gods – which was mankind’s

For time immemorial, nature has made noble metals part of our
daily life. The development of techniques for the controlled synthe-
sis of nanoparticles of well-defined size, shape and composition, to
be used in biomedical field and areas such as optics and electronics,
is a big challenge [1]. The application of noble metal nanoparticle
based chemistry for drinking water purification has been summa-
rized for different types of contaminants very recently [2]. It is
reported that small sized silver nanoparticles are able to easily pen-
etrate across membranes [3,4]. Further, a nanocrystal having higher
concentration of (1 1 1) facet is found to exhibit higher antibac-
terial activity [4]. The biosynthesis of nanoparticles has received
increasing attention due to the growing need to develop environ-
mentally benign technologies in material synthesis. There have
been numerous reports on the synthesis of metal nanoparticles
using microbes and plant materials as nanofactories [5–11]. The
potential and promises of plant system in biologically assisted
synthesis of metal nanoparticles in the name of green synthesis
is a key issue in nanoscience research [12]. Very recent reports
include the use of coriander leaf [9], henna leaf [10] and edible
mushroom [11] in the biosynthesis of Au and Ag nanoparticles.
Environmentally benign method for the preparation of Au, Ag and
Au–Ag nanoparticles in water, using glucose as reducing agent and
starch as protecting agent has been reported by Raveendran et al.
[13]. Green and shape controlled synthesis of gold and platinum
nanomaterials using vitamin B2 has also been carried out [14].
∗ Tel.: +91 471 2530887.
E-mail addresses: daizyp@rediffmail.com, philipdaizy@yahoo.co.in.
only sweetner for centuries is one of the world’s healthiest foods.
Its major constituents are fructose and glucose and it contains
aminoacids that help build up Ca in the body. Honey has been
subjected to extensive study [15–19] all over the world on its ingre-
dients, physicochemical properties, vitamins, mineral content and
quality control. It is reported to benefit human longevity due to its
high energy, presence of chemical elements, vitamins and enzymes.
Honey is rich in vitamin C and the important minerals present are
K and Mg. Also, it contains ingredients that can function as anti-
oxidants which play a vital role in the prevention of cancer. The use
of honey in the synthesis of gold nanoparticles has been reported
very recently [20]. Here, it is a report on a simple, cost-effective and
environmentally benign synthesis of very small silver nanoparti-
cles in water at ambient conditions using natural honey with its
ingredients acting as reducing and protecting agents.
2. Experimental
Natural honey procured from Kerala Agriculture University and
Ag NO3 (Sigma–Aldrich) were used as such. 20 g of honey was dis-
solved in 80 mL deionized water. 15 mL of this honey was added
to 20 mL aqueous solution of AgNO3 (10−3 M) and stirred well for
1 min. To initiate the reduction of Ag ions, the pH was adjusted to 6.5
using NaOH. Reduction takes place rapidly as indicated by golden
yellow colour of the solution which gives colloid s1 . Colloids s2 , s3 ,
s4 and s5 are obtained by adjusting the pH of the solution to 7, 7.5,
8 and 8.5. These colloids are found to be stable for about 6 months.
The UV–visible spectra were recorded on a JascoV-550
UV–vis spectrophotometer. X-ray diffraction (XRD) pattern of dry
nanoparticle powder was obtained using Siemens D5005 X-ray
diffractometer with Cu K␣ radiation ( = 0.1542 nm). The FTIR spec-

1386-1425/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2009.12.058
 D. Philip / Spectrochimica Acta Part A 75 (2010) 1078–1081
Fig. 1. UV–visible spectra of colloids: (a) s1 , (b) s2 , (c) s3 , (d) s4 and (e) s5 .
tra were obtained on a Nicolet 5700 FTIR spectrometer with the
samples as KBr pellets. The morphology of the nanoparticles was
analyzed using the high-resolution image obtained with a JEOL
3010 transmission electron microscope.
3. Results and discussion
Honey contains the reducing agents fructose, glucose and vita-
min C. Reduction of Ag ions takes place on the addition of NaOH.
The base facilitates the opening of the glucose ring by the abstrac-
tion of the ␣-proton of the sugar ring oxygen and the metal ions
oxidize glucose to gluconic acid [13]. It is also possible that sucrose
and proteins/enzymes play a role in the reduction. However, the
ingredient responsible for the reduction of Ag ions needs further
study.
3.1. UV–visible and TEM studies
Fig. 1 shows the UV–vis spectra of silver colloids s1 , s2 , s3 , s4
and s5 obtained at different pH values. At lower pH (Fig. 1(a) and
(b)) the surface plasmon resonance (SPR) band is broad indicating
poly-dispersed nanoparticles. As the pH is increased, the SPR band
gets sharpened and finally in colloid s5 at a pH of 8.5 (Fig. 1(e)) a
smooth and narrow absorption band at 413 nm is observed which is
Fig. 2. TEM images of colloids: (a) s2 and (b) s4 .
1079
characteristic of monodispersed spherical nanoparticles. The TEM
images obtained for colloids s2 , s4 and s5 are shown in Figs. 2 and 3.
Colloids s2 and s4 consist of large nanoparticles (Fig. 2). It is clear
from the TEM images in Figs. 2 and 3 that the particle size decreases
as the pH is increased and finally in colloid s5 nearly spherical par-
ticles of average size 4 nm is obtained. The typical high-resolution
TEM image (Fig. 3(d)) with clear lattice fringes having a spacing of
0.24 nm reveals that the growth of Ag nanoparticles occurs prefer-
entially on the (1 1 1) plane. The broad SPR bands observed at lower
pH values are due to large anisotropic particles. At lower pH values
growth is favoured due to the absence of sufficient gluconic acid
molecules and the SPR is broad indicating particles of larger size as
evidenced in Figs. 2 and 3. With the addition of more NaOH (that is,
as pH is increased), more gluconic acid is produced from glucose,
which in turn results in the reduction of Ag ions rapidly and forms
large number of very small nanoparticles giving rise to sharp and
intense SPR.
3.2. XRD and FTIR studies
The crystalline nature of silver nanoparticles was confirmed
from XRD analysis. Fig. 4 shows the XRD pattern of Ag nanoparti-
cles obtained using honey. The diffraction peaks appearing at 38.3◦ ,
44.6◦ , 64.8◦ , 77.9◦ and 81.2◦ correspond to the (1 1 1), (2 0 0), (2 2 0),
(3 1 1) and (2 2 2) facets of the face centered cubic crystal struc-
ture, respectively [8,21,22]. The ratio between the intensity of the
(2 0 0) and (1 1 1) diffraction peaks of 0.33 is lower than the conven-
tional bulk intensity ratio (0.52), suggesting that the (1 1 1) plane is
the predominant orientation as confirmed by high-resolution TEM
measurements. The average crystallite size according to Scherrer
equation calculated using the width of the (1 1 1) peak is found to
be 6 nm nearly in agreement with the particle size obtained from
TEM image of colloid s5 .
The important ingredients of honey are fructose, glucose,
sucrose, proteins, minerals and vitamins [15–19]. FTIR mea-
surement was carried out to identify the possible biomolecules
responsible for capping and efficient stabilization of Ag nanopar-
ticles synthesized using honey. Fig. 5 shows the FIR spectrum of
Ag nanoparticles obtained in this study. A comparison of the FTIR
spectrum (in the region from 1800 to 1000 cm−1 ) of gold nanopar-
ticles [20] synthesized using honey with that of the present case
shows that the biomolecules responsible for capping and hence
efficient stabilization are different in the two cases. In the reported
IR spectrum [20] of Au nanoparticles, band due to C O stretching
mode is observed as an intense band at 1714 cm−1 . However, in
the case of Ag nanoparticles (Fig. 5), this band is absent. This indi-
1080 D. Philip / Spectrochimica Acta Part A 75 (2010) 1078–1081

Fig. 3. TEM images of colloid s5 : (a), (b) and (c) at different magnifications and (d) high-resolution TEM image showing a fringe spacing of 0.24 nm.

cates the absence of a –COOH group in the material bound to silver
nanoparticles. The amide I and II bands of proteins [11,20,23–26]
are expected to occur as prominent IR bands around 1660 and
1535 cm−1 , respectively. In the present case, the bands observed at
1601 and 1547 cm−1 arise from amide I and II bands, respectively.
These bands arise due to carboxyl stretch and N–H deformation
vibrations in the amide linkages of protein. Proteins can bind to
Ag nanoparticles like Au nanoparticles through free amine groups
or carboxylate ion of aminoacid residue in it [22,24,27]. The band
observed at 1312 cm−1 is due to C–O stretching mode. The obser-
vation of C–O stretch, amide I and II bands and the absence of
the band due to the stretching mode of C O in the IR spectrum
(Fig. 5) of Ag nanoparticles indicates the stabilization of the system
through the –COO− (caboxylate ion) groups of aminoacid residues
with free carboxylate groups in the protein [22,24,27]. The very
strong band at 1028 cm−1 arises from C–O–C symmetric stretch-
ing and C–O–H bending vibrations of protein in the honey. If the
stabilization occurred through free amine groups, the band due to

Fig. 4. XRD pattern of dried powder of silver nanoparticles. Fig. 5. FTIR spectrum of silver nanoparticles.
 D. Philip / Spectrochimica Acta Part A 75 (2010) 1078–1081
C O stretch would have showed up around 1700 cm−1 in the IR
spectrum.
4. Conclusions
Crystalline silver nanoparticles of size ∼4 nm are synthesized at
ambient conditions using aqueous solution of AgNO3 and honey at
a pH of 8.5. The possible reducing agent is glucose and the capping
material responsible for stabilization is proteins present in honey.
This green method has advantages like ease with which the process
can be scaled up and economic viability.
Acknowledgements
This research has been sponsored by the University Grants Com-
mission, New Delhi, under the Research Award scheme. The author
is grateful to Prof T. Pradeep, DST unit on Nanoscience, IIT, Madras,
for TEM measurements.
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