Materials Science and Engineering B 195 (2015) 9097

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Materials Science and Engineering B

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

Facile synthesis of silver nanoparticles and their application in dye

degradation
Siby Joseph a , Beena Mathew b,
a
b

Department of Chemistry, St. Georges College, Aruvithura, Kottayam 686122, Kerala, India
School of Chemical Sciences, Mahatma Gandhi University, Kottayam 686560, Kerala, India

a r t i c l e

i n f o

Article history:
Received 20 October 2014
Received in revised form 13 February 2015
Accepted 15 February 2015
Available online 27 February 2015
Keywords:
Microwave
Silver nanoparticle
Hexamine
Starch
Methyl orange
Rhodamine B

a b s t r a c t
The present article reports a simple, facile and eco-friendly method based on microwave irradiation for the
synthesis of silver nanoparticles in aqueous medium using starch as stabilizing agent and a new reducing
agent namely hexamine. The silver nanoparticles were characterized by UVvis, FTIR, XRD and HR-TEM
analysis. UVvis spectroscopic studies provided sufcient evidences for the formation of nanoparticles.
The role of starch in the synthesis and stabilization of the nanoparticles was obtained from FTIR studies.
The XRD and HR-TEM investigations clearly demonstrated the crystalline nature of the nanoparticles.
From the TEM images, the silver nanoparticles were found to be spherical and of nearly uniform size
with an average diameter of 18.2 0.97 nm. The nanoparticles showed excellent catalytic activity in the
degradation of methyl orange and rhodamine B by NaBH4 .
2015 Elsevier B.V. All rights reserved.

1. Introduction
Synthetic organic dyes are extensively used in various industries
such as textile, paper, plastic, food, cosmetic and pharmaceutical
[1]. The discharges from these industries result in substantial environmental pollution. Studies have shown that many of the dyes
are carcinogenic, mutagenic and harmful to the environment [2].
These coloured dyes are toxic to aquatic organisms and perturb the
aquatic life. Various physical, chemical and biological water treatment methods have been used for removing the dye wastes. These
include methods such as adsorption, membrane ltration, chemical oxidation and reduction, photochemical and electrochemical
treatment, anaerobic treatment etc. [38]. Since the dye pollutants are chemically stable, traditional water treatment methods
are found to be ineffective. They are highly resistant to microorganisms and hence the water soluble dyes are not generally
decolourized effectively by conventional biological treatment [9].
Recently, nanotechnology has been extended to the area of waste
water treatment [10]. Nanocatalysis has undergone a remarkable
growth in recent years and seems to be a revolution in the eld
of catalysis. Metallic nanoparticles exhibit physical and chemical
properties that differ considerably from those of the bulk materials

Corresponding author. Tel.: +91 9447145412; fax: +91 481 2731036.

E-mail addresses: sibyjoseph4@gmail.com (S. Joseph), beenamscs@gmail.com
(B. Mathew).
http://dx.doi.org/10.1016/j.mseb.2015.02.007
0921-5107/ 2015 Elsevier B.V. All rights reserved.

[11]. This is largely due to their nite size and large surface area to
volume ratio and the reactivity that depends mostly on their size.
The size dependent reactivity and large surface area have made
them efcient catalysts [12]. Several researchers have reported the
use of nanocatalysts for the effective removal of dye stuffs [1215].
Among metal nanoparticles, silver nanoparticles (AgNPs) continue to be interesting in nanotechnology due to their excellent
optical and electronic properties as well as their strong toxicity to
a wide range of microorganism. Several synthetic approaches have
been developed for the synthesis of silver nanoparticles including
chemical [16], photochemical [17], sonochemical [18], radiolytic
[19], polyol [20] and biological methods [21]. Most of these production routes involve the use of toxic chemicals and require harsh
reaction conditions. Among these, the most popular method for the
preparation of Ag colloids is still the chemical reduction of a silver
salt in presence of a stabilizing agent because of its short reaction
time. The synthesis and application of silver nanoparticles requires
the stabilization of them in suitable stabilizing systems. However,
the chemical reagents used as reducing and stabilizing agents in
this method are usually highly toxic and poses huge environmental
hazards which limits their utility.
In recent years, immense amount of research has been carried out in the area of nanosynthesis by using non-toxic and
easily available materials with the aim to reduce environmental
threats. Microwave-assisted synthesis of nanoparticles in aqueous
medium using green chemicals is receiving much consideration
in recent times due to the adherence of this method to the three

S. Joseph, B. Mathew / Materials Science and Engineering B 195 (2015) 9097

principles of green nanoparticle synthesis which are (i) the selection of a non-toxic reducing agent, (ii) a cost-effective and easily
renewable stabilizing agent and (iii) an environmentally benign
solvent system. Furthermore it has several attractive features over
conventional thermal heating methods such as short reaction
time, lower energy consumption and better product yield [22].
Microwave irradiation offers rapid and uniform heating of the
reaction medium and thus provides homogeneous nucleation and
growth conditions for nanoparticles. Many successful reports on
microwave-assisted green synthesis of silver nanoparticles have
been published in recent years [2326].
In this work, we report the microwave-assisted synthesis of silver nanoparticles in aqueous medium using a new reducing agent
namely hexamine in presence of starch as stabilizing agent. Hexamine is a low-cost chemical that nds application in medicine
and food industry. It has been observed that when a strong reducing agent like NaBH4 is used, the reaction is very fast and has to
be cooled to control the rate of reduction in many cases. Moreover, it is highly toxic and synthesis of larger nanoparticles has been
found to be difcult [27]. On the other hand, when a mild reducing agent like sodium citrate or ascorbic acid is used, the reduction
reaction is slow and has to be carried out at elevated temperatures
to enhance the rate of reduction. In addition, they usually yield
relatively larger nanoparticles of varying size and shape [28]. In
contrast, hexamine is non-toxic, easy to handle, and yields spherical nanoparticles with narrow size distribution at a moderately
fast rate. Since all materials used in this method are environment
friendly, this may be regarded as a green approach for nanoparticle
synthesis. In addition, this method is simple, fast and economic. We
have investigated the catalytic utility of the starch stabilized silver
nanoparticles (AgNP-starch) in the dye degradation reactions by
taking the reduction reactions of methyl orange and rhodamine B
by NaBH4 as model reactions.
2. Materials and methods
2.1. Materials
Silver nitrate (AgNO3 ), hexamine, methyl orange, rhodamine
B and sodium borohydride (NaBH4 ) were purchased from Merck
India Ltd and used without further purication. All aqueous solutions were made by using double distilled water.
2.2. Methods
2.2.1. Synthesis of silver nanoparticles (AgNPs)
To 90 mL of aqueous solution containing 0.1 g starch which was
taken in a 250 mL beaker, 10 mL 0.05 M AgNO3 solution was added
in a drop wise manner and was stirred for 15 min. Followed by this,
0.028 g (0.002 M) hexamine was added and the reaction mixture
was subjected to microwave irradiation for 4 min by placing in a
domestic microwave oven (Sharp R-219T (W)) operating at a power
of 800 W and frequency 2450 MHz. The nanoparticle formation was
monitored using UVvis spectrophotometer by scrutinizing the
reaction mixture after 1, 2, 3 and 4 min of microwave irradiation
in the scan range 300700 nm. Upon microwave irradiation, the
colour of the reaction medium changed into yellowish-brown due
to nanoparticle formation.
2.2.2. Catalytic reduction of methyl orange
The catalytic reduction of methyl orange by NaBH4 was studied as follows. To 2 mL of aqueous methyl orange solution
(0.01 102 M) taken in a quartz cell of 1 cm path length, 0.5 mL
recently prepared NaBH4 solution (0.06 M) was added. Then 0.5 mL
of AgNP-starch colloidal solution of a denite concentration was
added to start the reaction. The variation in the concentration of

91

methyl orange with time was monitored using UVvis spectrophotometry by following the change in the absorbance of the peak at
464 nm. The absorption spectra were recorded in 1 min intervals in
the range of 200600 nm at ambient temperature.
2.2.3. Catalytic reduction of rhodamine B
To study this reaction, 0.5 mL freshly prepared NaBH4 solution
(0.06 M) was added to 2 mL of rhodamine B solution (0.06 103 M)
contained in a quartz cuvette. Subsequently, 0.5 mL of nanocatalyst
solution of a denite concentration was added and UVvis spectra
were recorded every 1 min in the range of 300700 nm. The kinetics
of the reaction was studied by measuring the change in intensity
of the peak at 554 nm with time.
2.2.4. Characterization
UVvis spectroscopic studies were carried out on a Shimadzu
UV-2450 spectrophotometer. FTIR spectra were recorded using
Perkin Elmer-400 spectrometer with ATR facility. The sample for
XRD measurement was prepared by depositing a thin lm of the
sample on a microscopic glass slide and the diffraction pattern
was recorded on a PANalytic XPERT-PRO X-ray spectrometer. High
resolution-transmission electron microscopic (HR-TEM) measurements were done using a JEOL JEM-2100 microscope.
3. Results and discussion
3.1. Synthesis and UVvis spectroscopic investigation of silver
nanoparticles
UVvis spectrophotometric analysis is used to follow and
conrm the formation of starch stabilized silver nanoparticles
(AgNP-starch). The reduction of Ag+ ions into Ag nanoparticles
was monitored by recording the absorption spectrum of the reaction mixture with time in the range of 300700 nm. The spectra
obtained during the synthesis AgNP-starch are depicted in Fig. 1. It
is well known that silver nanoparticles show an absorption band in
the range of 350450 nm due to surface plasmon vibrations of conducting electrons [29]. As is evident, initially no band was observed
in the range 350450 nm. But after 2 min of microwave heating,
the colourless solution began to change into yellowish brown and
a small absorption band appeared around 409 nm suggesting the
formation of silver colloids. The intensity of this absorption band
increased rapidly with increase in reaction time up to 4 min due to
the continuous formation of silver nanoparticles.
However, further increase in reaction time did not cause any
appreciable change in the intensity of the SPR band. The sharp

Fig. 1. UVvis absorption spectra recorded at 1 min interval during the course of
microwave-assisted AgNP-starch synthesis.

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S. Joseph, B. Mathew / Materials Science and Engineering B 195 (2015) 9097

Fig. 2. Schematic representation of the synthesis of AgNP-starch under microwave irradiation.

intense band suggests the formation of monodispersed and spherical nanoparticles and the absence of any peak in the range of
450700 nm indicates the lack of nanoparticle aggregation [30,31].
The stability of the synthesized AgNP-starch was conrmed by taking its UVvis absorption spectrum after storage for several months.
The absorption spectrum did not show any appreciable change in
the shape as well as wavelength of the SPR band. The SPR band
is sensitive to size and morphology of the nanoparticles [31]. This
clearly rules out the possibility of aggregation of the nanoparticles
upon storage and hence indicates the stability of the starch capped
silver nanoparticles.
The polymer chain of starch is rich in hydroxyl groups. So they
can easily attract the Ag+ ions towards it through electrostatic interaction and play a key role in the reduction process. The silver atoms
produced as a result of reduction by hexamine act as nucleation
centres and subsequently the Ag atoms coalesce leading to the formation of nanosized metal clusters. Once silver nanoparticles could
have grown, the OH groups behave as a docile contact for the silver nanoparticles and thus protect them from further coalescence
(Fig. 2). The reaction mixture is warmed up uniformly and instantaneously during microwave heating which helps in preventing the
aggregation of the particles. Even though silver is a noble metal, this
method of nano synthesis seems to be economic. This is because
all other chemicals used in this method are inexpensive and the
amount of AgNO3 used is very small which is almost quantitatively
converted to AgNP.
To establish the role of hexamine as reducing agent in this
synthesis process, a control experiment was performed under the
same conditions without using hexamine. Only a faint change was
observed in the colour of the reaction mixture even after irradiation for 4 min. The UVvis spectra obtained at 1 min intervals in
the control experiment are shown in Fig. 3. As is evident from the
gure, we can see only a slight change in the absorbance with time.
Thus it follows that starch by itself is unable to reduce Ag+ ions to
Ag by an appreciable extent.

Fig. 3. UVvis absorption spectra recorded at 1 min intervals during the microwave
synthesis of AgNP-starch without using hexamine.

To study the role of starch in the synthesis of stable nanoparticles, a control experiment was also conducted under the same
conditions in the absence of starch. Upon microwave irradiation,
instead of a yellowish brown coloured solution, a greyish white
residue was obtained. Furthermore, the UVvis spectrum of the
resulting solution did not show any absorption in the 300700 nm
region. Hence it follows that, the silver nanoparticles are not stable
in the absence of starch. Hexamine acts only as a reducing agent
and is not able to stabilize the nanoparticles. Silver nanoparticles
because of their highly reactive nature, coalesce into a residue in
the absence of starch. This clearly demonstrates the role of starch
as a capping agent in the synthetic process.
The concentration of silver nitrate used in the feed mixture for
the synthesis of AgNP has largely affected the outcome of nanoparticle synthesis. The intensity of the SPR band as well as the size of
silver nanoparticles were found to increase with increase in AgNO3
concentration in the reaction mixture. This may be explained on
the basis of the fact that, as the concentration of AgNO3 in the
reaction medium increases, the number of Ag+ ions available for
reduction by hexamine also increases. This enhances the chance of
collision between the silver atoms which in turn affects the growth
process [32]. As a result, the size of silver nanoparticles increases
with increase in AgNO3 concentration. It is also possible to synthesize silver nanoparticles by heating the reaction mixture thermally
instead of using microwave irradiation. But the synthesis process
was found to be time consuming and yielded larger nanoparticles
with broader size distribution.
3.2. FTIR analysis
Further evidence for the formation and stabilization of silver nanoparticles is obtained from FTIR measurements. The FTIR
spectrum of starch and starch stabilized silver nanoparticles were
recorded in order to identify the functional groups of the biopolymer involved in the synthesis and stabilization of nanoparticles.
Fig. 4 shows the FTIR spectrum of starch and AgNP-starch. The

Fig. 4. FTIR spectra of (a) starch, and (b) AgNP-starch.

S. Joseph, B. Mathew / Materials Science and Engineering B 195 (2015) 9097

major peaks present in the spectrum of starch were observed

at 3290, 2918, 1350 and 996 cm1 respectively. The broad peak
observed at about 3290 cm1 corresponds to O H stretching vibrations of hydroxyl group. The peak at 2918 cm1 could be assigned
to stretching vibrations of aliphatic C H groups. The peaks at 1350
and 996 cm1 can be attributed to C O and C O C stretching
vibrations respectively. The spectrum of AgNP-starch showed the
above mentioned peaks at 3300, 2927, 1368, and 1004 cm1 respectively.
Compared with starch, the vibration peaks of AgNP-starch are
shifted to higher wave numbers. This observation clearly conrms
the successful capping of silver nanoparticles by starch. Moreover, a new peak was observed at 1740 cm1 in the spectrum of
AgNP-starch. This peak is assigned to C O stretching vibrations of
carbonyl groups which are formed from the oxidation of hydroxyl
groups. This shows the involvement of O H groups of starch along
with hexamine in the reduction of Ag+ ions into Ag atoms. Further
evidence for the effective capping of the silver nanoparticles by the
starch molecules is obtained from the HR-TEM images (Fig. 6).

93

Fig. 5. XRD pattern of AgNP-starch.

3.4. High resolution-transmission electron microscopy (HR-TEM)

studies
3.3. XRD study
X-ray diffraction studies were conducted to obtain information
about the crystalline nature of nanoparticles. The XRD pattern of
AgNP-starch (Fig. 5) clearly shows four diffraction peaks at 38.30 ,
44.47 , 64.86 , and 77.98 which can be indexed respectively to the
(1 1 1), (2 0 0), (2 2 0), and (3 1 1) crystallographic planes of fcc silver
nanoparticles. The intensity of the peak due to the reection from
(1 1 1) Bragg plane is higher than that of other planes due to the
preferential adsorption of Ag atoms on (1 1 1) plane during crystal growth. This diffraction pattern is in good agreement with the
standard diffraction pattern of JCPDS le no. 04-0783. Thus X-ray
diffraction studies undoubtedly demonstrate the crystalline nature
of the synthesized silver nanoparticles.

The size and morphology of the synthesized silver nanoparticles were examined using transmission electron microscopy (TEM)
analysis. The typical TEM images of AgNP-starch are given in Fig. 6.
The images show that the nanoparticles synthesized using starch
as stabilizing agent are almost spherical and of nearly uniform size.
The histogram representing the size distribution of the particles
(Fig. 6(d)) obtained by analyzing the images support this observation. The average size of the particles is found to be 18.2 0.97 nm
and the size of the nanoparticles varies between 16 and 21 nm.
Almost 75% of the nanoparticles have size between 17 and 19 nm,
19% in the range of 1920 nm and a very small percentage of the
nanoparticles have size above and below the range of 1720 nm.
The representative high resolution TEM (HR-TEM) image (Fig. 6(e))

Fig. 6. (ac) TEM images of AgNP-starch at different magnications, (d) the corresponding particle size histogram, (e) high resolution TEM image, and (f) the selected area
electron diffraction (SAED) pattern.

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S. Joseph, B. Mathew / Materials Science and Engineering B 195 (2015) 9097

Fig. 7. Chemical structure of methyl orange.

with clear lattice fringes indicates the high crystallinity of nanoparticles. The spacing between the lattice planes was measured as
This distance is in good agreement with the lattice spacing
2.34 A.
of (1 1 1) planes of fcc silver. The selected area electron diffraction
(SAED) pattern (Fig. 6(f)) once again conrms the crystalline nature
of the nanoparticles. The bright circular spots observed in the electron diffraction pattern corresponds to (1 1 1), (2 0 0), (2 2 0), and
(3 1 1) reection planes.
3.5. Catalytic degradation of methyl orange
The reduction of organic dyes by excess of NaBH4 is widely used
for evaluating the catalytic efciency of metal nanoparticles provided their reduction reaction is thermodynamically favourable but
not kinetically and their major spectral bands do not overlap with
the SPR band of metal nanoparticles [33]. Methyl orange (MO) is
an organic azo dye which is commonly used as an indicator in various analytical elds (Fig. 7). Since methyl orange generates several
environmental and health problems, its degradation and removal
is of very interest.
The aqueous solution of methyl orange is orange red in colour.
The UVvis spectrum of aqueous solution shows strong absorptions
at 464 nm and 264 nm. The max at 464 nm is due to the absorption
of N N group. Since the max of methyl orange is well separated
from the surface plasmon absorption of silver nanoparticles, this
catalytic reaction can be easily followed spectrophotometrically.
The reduction of methyl orange by NaBH4 in the absence of
AgNP-starch catalyst is insignicantly slow. This is evident from the
observation that the intensity of max at 464 nm remains virtually
unchanged for several hours when a blank experiment is performed without AgNP catalyst. Thus this reaction is not kinetically
favourable in the absence of the catalyst and could not be realized
only with NaBH4 . But the degradation reaction started immediately
upon the addition of the catalyst. This is apparent from the fading
of the orange colour of the reaction medium as well as the decrease
in intensity of the peak at 464 nm. The reduction of methyl orange
by NaBH4 results in the reduction of azo group ( N N ) of methyl
orange thereby yielding the corresponding amino compounds. The
kinetics of AgNP-starch catalyzed degradation of methyl orange
by NaBH4 was studied spectrophotometrically by monitoring the
change in intensity of the absorption peak at 464 nm. Fig. 8 shows
the UVvis spectra recorded at 1 min intervals for the reduction

Fig. 8. UVvis absorption spectra for the reduction of methyl orange by NaBH4
catalyzed by 0.015 mg/mL AgNP-starch at 24 C recorded at 1 min intervals.

Fig. 9. Schematic diagram showing the catalytic degradation of organic dyes by

AgNP-starch.

of MO catalyzed by AgNP-starch of concentration 0.015 mg/mL at

24 C.
As soon as the catalyst was added, the absorbance at 464 nm
decreased continuously with time. This was accompanied by the
concomitant appearance and growth of a new peak at 250 nm.
This peak appeared during the course of the reaction is attributed
to the NH2 group absorptions of the product molecules. With
the decrease in intensity at 464 nm, the intensity of the product
peak was found to increase with passage of time. The reaction was
completed in 10 min as was evident from almost zero absorption
at 464 nm. After the completion of the reaction, a weak absorption band was observed at 398 nm. This is believed to be the SPR
band of nano silver catalyst. At intermediate stages of the reaction, this weak band is obscure as this is covered by the strong
absorption band of methyl orange which extends over the range
of 350600 nm. But during the catalytic process, the SPR band of
AgNP undergoes a blue shift from 409 nm to 398 nm. This provides
a clear evidence for the electron relay process occurring during the
reduction reaction. Electron transfer play the crucial role in the
degradation of methyl orange. The large difference in redox potential between the donor borohydride ion and the acceptor methyl
orange hinders the electron transfer between them [34,35]. Thus
the reduction of methyl orange by NaBH4 in the absence of the
nanocatalyst is thermodynamically favourable and not kinetically.
AgNP catalyst provides an alternative path of low activation energy
for the reaction and hence reduces the kinetic barrier thereby making it thermodynamically as well as kinetically favourable [36].
Upon addition of the catalyst, the borohydride ions which donates
the electrons and methyl orange which accepts the electrons gets
adsorbed on the surface of the nanocatalyst. The starch molecules
which cap the nanoparticles help in bringing the reactants closer
to the catalyst surface. The reduction occurs by the transfer of electrons from borohydride ions to methyl orange. Silver nanoparticles
help this electron shuttling process by relaying electrons from the
donor to the acceptor (Fig. 9). The blue shift observed in the position
of the SPR band of AgNP is attributed to the surface modication
that occurs to the nanoparticles due to the electron relay process
[37] and also to the interaction between the absorption peak of
methyl orange and SPR band of AgNP which overlap one another.
In this reaction, the concentration of NaBH4 was adjusted to
exceed largely that of methyl orange and the catalyst. As the concentration of NaBH4 is very high, it remains practically constant
during the reaction. Therefore pseudo-rst order kinetics with
respect to methyl orange could be used in this case to evaluate the
kinetics of the reaction. The reaction kinetics can be represented
using the equation ln [A]/[A0 ] = kt, where k is pseudo-rst order
rate constant, t is the reaction time, [A0 ] is the concentration of

S. Joseph, B. Mathew / Materials Science and Engineering B 195 (2015) 9097

Fig. 10. Plots of ln [A] against time for the reduction of methyl orange using
varying concentrations of AgNP-starch at 24 C. Conditions: [MO] = 0.01 102 M,
[NaBH4 ] = 0.06 M.

methyl orange at time t = 0 and [A] is the concentration at time t

which can be obtained from the absorbance of the peak at 464 nm.
To study the effect of nanocatalyst concentration upon rate of the
reaction, the degradation reaction was carried out using varying
concentration of AgNP-starch, keeping other parameters constant.
The relationship between ln [A] and time for the reduction of
methyl orange using different concentration of the nanocatalyst
are given in Fig. 10. A linear relationship was obtained in all cases
conrming the pseudo-rst order nature of the reaction. The rst
order rate constants can be evaluated directly from the slope of
these plots. A small induction time was observed for all the reactions studied when carried out under air and this was found to
decrease with increase in amount of the catalyst. The induction
time may be caused by the reduction of O2 present in the reaction medium which takes place faster than the reduction of methyl
orange and also may be the time required for the NaBH4 molecules
to eliminate oxides from the catalyst surface and thus to activate
the catalyst [3740].
The rst order rate constant obtained from the slope of ln [A]
versus time plot for different catalysts and the corresponding correlation coefcients are given in Table 1. It is clear from the table that,
all the reactions are very fast. They strictly adhere to pseudo-rst
order kinetics as is evident from the values of correlation coefcient.
With increase in the concentration of silver nanoparticle catalyst in the reaction system, a rapid increase in rate and hence rate
constant of the reactions was observed (Fig. 11). This is attributed
to the fact that as the concentration of AgNP in the reaction medium
increases, the catalyst surface available for adsorption of the reactants also increases. This in turn enhances the speed of degradation
process.
3.6. Catalytic degradation of rhodamine B
The catalytic performance of AgNPs was also evaluated using
the reduction reaction of rhodamine B by NaBH4 . Rhodamine B
(RhB) is a uorescent dye belonging to the family of xanthenes

95

Fig. 11. Plot of rate constant (k) against concentration of catalyst for the reduction
of methyl orange at 24 C.

Fig. 12. Chemical structure of rhodamine B.

(Fig. 12). Rhodamine dyes are widely used as uorescent probes

owing to their high absorption coefcient and broad uorescence in
the visible region of electromagnetic spectrum. Due to their excellent photostability and photophysical properties, they are used as
laser dyes and for imaging in living cells [41]. Moreover, it is widely
used in textile industry and forms an important dye pollutant.
This reaction is selected for catalytic study because the redox
potential of Ag nanoparticles is in between those of RhB (0.48 V)
and NaBH4 (1.33 V). So AgNPs can act as electron transfer agents
and relay electrons from the donor NaBH4 to the acceptor RhB
dye. The aqueous solution of rhodamine B is pink red in colour.
The UVvis absorption spectrum of rhodamine B exhibits strong
absorptions in the range of 200700 nm with max at 554 nm
(Fig. 13). Thus the max of RhB is well separated from the SPR
oscillations of AgNP-starch and this makes the kinetic study easy.
The degradation reaction of RhB can be kinetically followed by
examining the absorbance value of the peak at 554 nm as a function
of time. The UVvis absorption spectra recorded during the reduction reaction of RhB by NaBH4 in presence of AgNP-starch catalyst
of concentration 0.04 mg/mL at 24 C is given in Fig. 14. The successive spectra were measured at an interval of 1 min. The reaction was
very insignicant in the absence of AgNP catalyst. But the reduction
of RhB started immediately upon the addition of the catalyst as evidenced by the gradual disappearance of the pink red colour of RhB.

Table 1
Pseudo-rst order rate constants for the reduction of methyl orange catalyzed by AgNP-starch.
Conc. of AgNP (mg/mL)

Reaction time (min)

k 103 (s1 )

Correlation coefcient (R2 )

0.015
0.025
0.035
0.050

10
08
06
04

2.22
4.04
6.22
8.28

0.9975
0.9971
0.9934
0.9886

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S. Joseph, B. Mathew / Materials Science and Engineering B 195 (2015) 9097

Fig. 13. UVvis absorption spectrum of rhodamine B.

The reactions was completed in 9 min. The peak observed at 406 nm

is characteristic of the surface plasmon oscillations of Ag nanocatalyst. This peak has undergone a blue shift in its position from 409
to 406 nm. But this shift is less than that observed in case of methyl
orange degradation. This may be attributed to the fact that the max
of RhB is detached from the SPR absorption of AgNP catalyst and
this reduces the possibility of interaction between these two peaks.
Initially, a small induction time was observed in this case too. This
was found to decrease with increase in temperature and catalyst
dosage.
For the evaluation of the catalytic rate, pseudo-rst order kinetics with respect to the concentration of RhB is assumed in this case
also since the concentration of NaBH4 used essentially exceeds that
of RhB. The pseudo-rst order plot obtained for the above reaction
by measuring the absorbance value at 554 nm as a function of time
is depicted in Fig. 15.
A linear plot with correlation coefcient (R2 ) value of 0.9942 was
obtained and the value of pseudo-rst order rate constant obtained
from the slope of the above plot was found to be 2.99 103 s1 .
The mechanism of this reaction also involves an electron transfer
process. With respect to AgNP, BH4 ion is nucleophilic and RhB is
electrophilic in nature. Right after the adsorption of both BH4 ions
and RhB on the catalyst surface, the AgNPs transfer electrons from
the donor BH4 ions to the acceptor RhB molecules. As a result, the
pink red coloured rhodamine B is reduced to leuco rhodamine.
In order to study the reusability of the AgNP catalyst in the
dye degradation reactions, the nanocatalyst was recovered from
the reaction mixture at the end of the reaction by centrifugation
and was dispersed in double distilled water to remove any species
adhering to their surface. The rate of degradation of both methyl
orange and rhodamine B was found to be more or less the same
for the rst and second cycle but decreased from the third cycle

Fig. 15. Plot of ln [A] versus time for the NaBH4 reduction of rhodamine B using
0.04 mg/mL AgNP-starch at 24 C.

onwards. This observation is attributed to the deactivation of the

active reaction sites on the catalyst surface due to repeated adsorption of the reactants [39].
4. Conclusions
In the present study, we have reported a simple, one pot, and
economic method for the green synthesis of silver nanoparticles in
aqueous medium. Microwave assisted synthesis using hexamine
as the reducing agent and starch as the stabilizer appears to be an
effective method for the large scale production of uniform sized
silver nanoparticles. The nanoparticles were found to be stable
in aqueous medium under ambient conditions even after storage
for several months. The nanoparticles were characterized using
UVvis, FTIR, XRD, and HR-TEM analysis. This new method for
nanosynthesis produced well dispersed and highly crystalline silver nanoparticles with an average diameter of 18.2 0.97 nm. The
catalytic ability of the synthesized nanoparticles was investigated
using the degradation reactions of methyl orange and rhodamine
B by NaBH4 . The catalyst showed outstanding catalytic activity
in these dye degradation reactions. The reactions were very fast
and followed pseudo-rst order kinetics. Thus this new synthetic
method affords a very efcient route for the generation of highly
stable spherical silver nanoparticles which nd application as effective catalyst for the degradation of organic dyes from various
industrial efuents.
Acknowledgment
The nancial assistance provided by UGC (under FIP Scheme),
Government of India is gratefully acknowledged.
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Fig. 14. Successive UVvis spectra measured at 1 min intervals during the catalytic
degradation of rhodamine B using 0.04 mg/mL AgNP-starch at 24 C.

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