Micron 56 (2014) 5462

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Micron
journal homepage: www.elsevier.com/locate/micron

Catalytic degradation of organic dyes using biosynthesized silver

nanoparticles
V.K. Vidhu, Daizy Philip
Department of Physics, Mar Ivanios College, Thiruvananthapuram 695 015, India

a r t i c l e

i n f o

Article history:
Received 6 September 2013
Received in revised form 10 October 2013
Accepted 10 October 2013
Keywords:
Silver nanoparticles
Trigonella foenum-graecum
Catalysis
Methylene blue
Methyl orange
Eosin Y

a b s t r a c t
The green synthesis of metallic nanoparticles paved the way to improve and protect the environment by
decreasing the use of toxic chemicals and eliminating biological risks in biomedical applications. Plant
mediated synthesis of metal nanoparticles is gaining more importance owing to its simplicity, rapid rate
of synthesis of nanoparticles and eco-friendliness. The present article reports an environmentally benign
and unexploited method for the synthesis of silver nanocatalysts using Trigonella foenum-graecum seeds,
which is a potential source of phytochemicals. The UVvisible absorption spectra of the silver samples
exhibited distinct band centered around 400440 nm. The major phytochemicals present in the seed
extract responsible for the formation of silver nanocatalysts are identied using FTIR spectroscopy. The
report emphasizes the effect of the size of silver nanoparticles on the degradation rate of hazardous dyes,
methyl orange, methylene blue and eosin Y by NaBH4 . The efciency of silver nanoparticles as a promising
candidate for the catalysis of organic dyes by NaBH4 through the electron transfer process is established
in the present study.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
The development of nanotechnology has become an important
issue for scientic exploration in physics, chemistry and engineering. In this context metal nanoparticles present some distinct
features that are directly related to particle size and shape. Metal
nanoparticles especially silver nanoparticles are found suitable
candidates in applications such as medical diagnosis (Jain et al.,
2008), drug delivery systems (Elechiguerra et al., 2005), sanitization
(Krishnaraj et al., 2010), water treatment (Li et al., 2008) and wound
healing (Tian et al., 2007). Currently, sustainability initiatives that
use green chemistry to improve and protect our global environment are becoming focal issues in many elds of research. This
has paved the way for the greener synthesis of nanoparticles and
has proven to be promising due to slower kinetics, better manipulation, control over crystal growth and their stabilization. This
has motivated an upsurge in research on the synthesis routes that
allow better control of shape and size for various nanotechnological applications. Instead of using toxic chemicals for the reduction
and stabilization of metallic nanoparticles, the use of various biological entities has received considerable attention in the eld of
nanobiotechnology. Among the many possible natural products,
biologically active plant products represent excellent scaffolds for
this purpose (Dubey et al., 2010a,b; Roopan et al., 2013). Among

Corresponding author. Tel.: +91 471 2531053; fax: +91 471 2530023.
E-mail addresses: philipdaizy@yahoo.co.in, daizyp@rediffmail.com (D. Philip).
0968-4328/$ see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.micron.2013.10.006

the various categories of compounds in plants that have potential

biological activities, phytochemicals are emerging as an important
natural resource for the synthesis of metallic nanoparticles. They
play important roles in both reduction and stabilization of nanoparticles.
The focus of the present work is to apply the factual principles of green chemistry in the synthesis of silver nanoparticles by
using stand alone reducing and capping agent as Trigonella foenumgraecum seeds with water as a solvent. Fenugreek is an annual herb
whose leaves and seeds are widely consumed in Indo-Pak sub continent as spice and medicine. Fleiss reported that fenugreek seeds
are used as galactagogue by nursing mothers to increase inadequate
breast milk supply (Fleiss, 1988). The diseases such as diabetes
and hypercholesterolemia can be treated using fenugreek seeds
(Basch et al., 2003; Miraldi et al., 2001). It is also reported that
fenugreek seeds exhibit pharmacological properties such as antitumor, antiviral, antimicrobial, anti-inammatory, hypotensive and
antioxidant activity (Cowan, 1998; Shetty and Labbe, 1998). The
synthesis method in the article is unique on its own till date. This
article reveals the possibility of producing highly monodispersed,
stable and colloidal silver nanoparticles.
Dyes are a major class of synthetic organic compounds released
by many industries such as paper, plastic, leather, food, cosmetic, textile and pharmaceutical industries (Kulkarni et al., 1985;
Zollinger, 1987). These efuents result in signicant environmental
pollution. Azo dye compounds were recognized as potential carcinogens (Chung and Cerniglia, 1992; Kusic et al., 2006). Abatement
of dyes is a required part of wastewater treatment. The dye efuents

V.K. Vidhu, D. Philip / Micron 56 (2014) 5462

are highly resistant to microorganisms so that their reduction by

using conventional biological treatment is generally ineffective and
also resistant to destruction by physicalchemical treatments in a
high efuent concentration. Nanotechnology has been extended
to the wastewater treatments in the recent years. Due to high surface area silver nanoparticles exhibits an enhanced reactivity (Kang
et al., 2000). In the present study, we have investigated the size
dependent catalytic degradation of organic dyes methyl orange,
methylene blue and eosin Y by NaBH4 in the presence of silver
colloids.
2. Materials and methods
Silver nitrate (99.99%), methyl orange, eosin Y, methylene blue
and sodium borohydride were procured from sigma Aldrich. All
glasswares were cleaned with aqua regia and rinsed several times
with de-ionized water.
2.1. Preparation of extract
T. foenum-graecum seeds were purchased from local market. 10 g
of T. foenum-graecum seeds was washed using deionised water several times and boiled with 100 mL of deionised water at 373 K for
2 min. The extract was ltered and used for further experiments.
2.2. Synthesis of silver nanoparticles
Silver nanoparticles (sample F1 ) have been synthesized by
adding 2 mL extract to preheated 30 mL 3.1 104 M silver nitrate
solution and boiled at 373 K for 2 min. The formation of silver
nanoparticles is indicated by the appearance of yellowish brown
color within 5 min. Samples F2 F5 were synthesized in the same
procedure by adding 5 mL, 8 mL, 10 mL and 15 mL extracts, respectively.
2.3. Catalysis
1 mL 100 mM sodium borohydride solution is added to 1 mL
103 M methyl orange (MO), methylene blue and eosin Y, respectively. The solutions are then made up to 10 mL using deionised
water and vigorously stirred for 5 min. Then 0.5 mL, 2 mL and 2 mL
of silver colloid (sample F1 ) is added to the solutions, respectively,
and stirred for ve more minutes. The degradation of dyes is indicated by the decolorisation of the solution.
Methylene blue initially blue in color in an oxidizing environment became colorless in the presence of reducing agent (NaBH4 )
indicating the reduction of methylene blue to leucomethylene blue
(LMB) (Leonard et al., 2011).
The effect of size variation on the degradation of dyes has been
investigated by performing the catalytic experiments using samples F3 and F5 . The reaction unsupported by the catalyst is a studied
as a reference. All the degradation process was monitored using
UVvisible absorption spectrophotometer.
3. Characterization
UVvisible spectra analysis was performed for all samples
and the absorption maxima were analyzed at a wavelength of
200700 nm using Lambda35 PerkinElmer Spectrophotometer. Deionised water was used for background correction of all
UVvisible absorption spectra. All samples were centrifuged several times using deionised water and loaded in a 1 cm path length
quartz cuvettte for sampling. FTIR spectra of nanocrystalline
sample and extract were recorded using IR Prestige-21 Schimadzu spectrometer. XRD pattern was recorded by XPERT-PRO

55

The scanning
diffractometer using Cu K radiation ( = 1.5406 A).
was performed in the region of 2 from 20 degrees to 90 degree.
The morphology of the silver nanoparticles was examined using
Tecnai G2 30Transmission Electron Microscope. The size dependent catalytic action of as prepared samples was examined by
monitoring the UVvisible spectra of the samples at a regular
interval of 1 min after adding the colloid.
4. Results and discussion
A well-accepted scientic consensus emanating from several
scientic investigations is that fenugreek seeds contain high levels
of antioxidant polyphenols, including avanoids (Sumayya et al.,
2012). The phenolics and other phytochemicals in the extracts
not only result in effective reduction of silver salts to nanoparticles but their chemical framework is also effective at wrapping
around the nanoparticles to provide excellent robustness against
agglomeration. The discovery of the unique chemical power of nontoxic phytochemicals in nanoparticles formation is of paramount
importance in the context of the production of silver nanoparticles for medical and technological applications under non-toxic
conditions.
The phytochemical analysis of fenugreek seeds reveal the
presence of carbohydrates, proteins, phenols, sterols, avanoids,
alkaloids, quinones, terpenoids, tannins, glycosides, saponins in
the fenugreek seed (Sumayya et al., 2012). Phenolic compounds
possess hydroxyl and carboxyl groups, which are able to bind to
metals (Harborn, 1988). The roots of many plants contain high levels of phenolic compounds which may inactivate ions by chelating.
According to Moran et al. (1997) the chelating ability of phenolic
compounds is related to the high nucleophilic character of the aromatic rings. Also, the excellent antioxidant activity of avanoids
resides mainly in their ability to donate electrons or hydrogen
atoms.
The protein present may cap the silver nanoparticles formed,
restricting the agglomeration of the particles and thus checking the
size and shape (Ahmad et al., 2010). Presumably biosynthetic products or reduced cofactors play an important part in the reduction
of ions to silver nanoparticles as the concept of antioxidant action
of phenol compounds is not new.
4.1. UVvisible spectra
The strong interaction of metal nanoparticles with light results
in the collective oscillation of the conduction electrons on the metal
surface, known as a surface plasmon resonance (SPR). The SPR
results in unusually strong scattering and absorption properties.
Due to the unique optical properties of silver nanoparticles, a great
deal of information about the physical state can be obtained by
analyzing the spectra. As the diameter increases, the peak plasmon resonance shifts to longer wavelengths and broadens. The
secondary band may be due to a quadrupole resonance that has
a different electron oscillation pattern than the primary dipole resonance. The band wavelength, the band width, and the effect of
secondary resonances yield a unique spectral ngerprint for a plasmonic nanoparticle with a specic size and shape. The UVvisible
absorption spectra of samples F1 F5 is shown in Fig. 1. The spectra reveal a strong dependence of absorbance on the quantity of
extract added. The spectra exhibits absorption bands in the range
400440 nm. The broad SPR can be attributed to the formation
of anisotropic particles. The spectra reveal a secondary band in
higher wavelength as the quantity of extract increases. For nonspherical metallic nanoparticles, the surface plasmons are unevenly
distributed which results in the shape dependent SPR absorption spectra (Sun and Xia, 2003). According to Mies theory small

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V.K. Vidhu, D. Philip / Micron 56 (2014) 5462

Fig. 1. UVvisible absorption spectra of samples F1 F5 .

spherical or quasi-spherical nanocrystals exhibit a single SPR band;

whereas anisotropic particles show two or three bands, depending
on their shape. Absorption spectra of larger metal colloidal dispersions can exhibit broad or additional bands in the UVvisible
range due to the excitation of plasma resonances or quadrupole or
higher multipole plasmon excitation (Mie, 1908). The anisotropy
of the particles seems increased with increase in the quantity of
extract.

Fig. 2. The X-ray diffraction pattern of silver nanoparticles.

4.2. XRD and HRTEM analysis

The XRD pattern of silver nanoparticles is as shown in Fig. 2.The
peaks at 38.36 , 44.74 , 64.85 , 77.75 and 81.85 are assigned
to diffraction from the (1 1 1), (2 0 0), (2 2 0), (3 1 1), and (2 2 2)
planes of face centered cubic silver (JCPDS le No. 87-0720). Also,
peaks corresponding to any impurity phase were absent in the
experimental diffraction pattern. The average crystal size of sil-

Fig. 3. (ad) TEM images of sample F2 at different magnications. The inset in Fig. 3(a) shows the particle size distribution of sample F2 .

V.K. Vidhu, D. Philip / Micron 56 (2014) 5462

57

Fig. 4. (ad) TEM images of sample F4 at different magnications.

ver nanoparticles is calculated from FWHM of the diffraction peaks

using Scherrer equation given below:
D=

0.9
cos 

(1)

where 0.9 is the shape factor,  is the X-ray wavelength, typically

is the FWHM in radians and  is the Bragg angle. The aver1.54 A,
age crystallite size calculated using Scherrers equation is 17 nm.
The application of TEM in nanoscience is signicant to view
the particles in nanoscale. The HRTEM images at different magnications of synthesized silver nanoparticles and SAED pattern
are depicted in the Figs. 35 which give clear indications regarding
size, shape and size distribution of nanoparticles. Fig. 3(ad) and
Fig. 4(ad) show the HRTEM images of sample F2 and sample F4 ,
respectively. The TEM images of sample F5 at different magnications is shown in Fig. 5(ad). From the images, it can be seen that
the silver nanoparticles are covered with extract. The layer around
the particles (Fig. 4c and Fig. 5c) may be the phytoconstituents
of extract used. The SAED pattern of silver nanoparticles reveals
its polycrystalline nature. The average particle size calculated for
samples F2 , F4 and F5 are 22 nm, 28 nm and 32 nm, respectively.
4.3. FTIR spectra
The FTIR spectra offer information regarding chemical changes
in the functional groups involved in the bioreduction. The seeds of

fenugreek contain lysine and l-tyrptophan rich proteins, mucilaginous ber and other rare chemical constituents such as saponins,
coumarin, fenugreekine, nicotinic acid, sapogenins, phytic acid,
scopoletin, trigonelline, gallic acid, tannins and quinones, which
are thought to account for many of its presumed therapeutic effects
(Sumayya et al., 2012; Billaud and Adrian, 2001; Sauvaire et al.,
1991; Ribes et al., 1986). It has been reported that the reducing power of bioactive compounds is associated with antioxidant
activity (Yldrm et al., 2001; Siddhuraju et al., 2002). According to Meir et al. (1995) the fenugreek has volatile oil, phenolic
acids and avanoids; therefore it is a potential source of vitamins.
The FTIR spectra of fenugreek seed extract and corresponding silver nanoparticles are shown in Fig. 6a and b. The bands at
1609 cm1 and 1618 cm1 in the spectra of nano silver and extract,
respectively, correspond to C C groups or aromatic rings (Shankar
et al., 2004) or C O stretching in carboxyl group (amide I band) of
proteins (Sheny et al., 2011). The band at 1057 cm1 correspond to
CN- stretching of amines. The IR band at 1412 cm1 can attributed
to geminal methyl (Kora et al., 2010).
The possible mechanism proposed for the reduction of Ag+ to
Ag nanoparticles is that Ag+ ions can form intermediate complexes
with phenolic OH groups present in hydrolysable tannins which
subsequently undergo oxidation to quinone forms with consequent reduction of Ag+ to AgNPs (Bulut and Ozacar, 2009; Edison
Immanuel and Sethuraman, 2012).

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V.K. Vidhu, D. Philip / Micron 56 (2014) 5462

Fig. 5. (ac) TEM images of sample F5 at different magnications (d) SAED pattern. The inset in Fig. 5(a) shows the particle size distribution of sample F5 .

4.4. Catalysis
4.4.1. Catalytic degradation of methyl orange
Today environmental protection has become more and more
important for human beings, and some toxic and stable dye
molecules like MO are dangerous to the environment (Wang et al.,
2008). MO is an organic sulfosalt dye, which can be reduced by
reductants like NaBH4 to form small organic molecules rstly and
non toxic species nally, but the reduction rate is very slow. Metal

nanoparticles with high reactive activity and specic surface area

can accelerate the reduction rate of dyes, thus increasing the reducing efciency.
Fig. 7a represents the compiled absorption spectra of degradation of methyl orange by NaBH4 in the absence of silver
nanoparticles. The spectral band of MO is known to appear at
465 nm. It can be observed that the blank experiments performed
without any silver catalysts show nearly no change in absorbance
of MO solution indicating that MO is not reduced effectively by

Fig. 6. Effect of extract on the formation of silver nanoparticles. FTIR spectra of (a) extract (b) silver nanoparticles.

V.K. Vidhu, D. Philip / Micron 56 (2014) 5462

59

Fig. 7. UVvisible absorption spectra of degradation of (a) methyl orange (b) methylene blue and (c) eosin Y by NaBH4 in the absence of silver nanoparticles.

Fig. 8. Effect of silver nanoparticles on the catalysis of methyl orange to hydrazine derivatives. UVvisible absorption spectra of degradation of methyl orange by NaBH4 in
the presence of (a) sample F1 (b) sample F3 and (c) sample F5 . The band corresponding to hydrazine derivatives emerges at 247 nm as the degradation proceeds.

NaBH4 or the reduction rate is very slow. The reduction of MO in

the presence of samples F1 , F3 and F5 is shown in Fig. 8ac, respectively. The reaction time is observed to be increasing with increase
in particle size. After adding silver nanoparticles (sample F1 ) to the
MO and NaBH4 solution, adsorption can take place between the
well-dispersed silver nanoparticles and MO molecules. The large
specic area of nanoparticles increases the reactivity. The layer of
reducing agent on the surface of silver nanoparticles may also promote the effective adsorption between silver nanoparticles and MO
molecules. As a consequence, the oxidation-reduction between the
active MO and NaBH4 can happen more easily, effectively and faster
for particles with smaller size.
The suggested mechanism involves the electron transfers from
NaBH4 to excited MO species and its subsequent reduction as
showed in the following mechanism:
Ag/NaBH4 + h Ag/NaBH4 (h+ -e )

(2)

2e + MOH+ + H+ MOH2 (Hydrazinederivatives)

(3)

The MO band at 465 nm gradually disappears and a new band

assigned to hydrazine derivatives grows at 247 nm. The detailed
reaction mechanism is not fully known, but likely involves both the
electron and hole that is produced at the same time. Both oxidation
and reduction may occur and may involve intermediates such as
hydroxyl radical (Peral et al., 1995).
4.4.2. Catalytic degradation of methylene blue
The use of methylene blue, a heterocyclic aromatic dye, in the
textile has increased in the last few years (Kang et al., 2000). The
UVvisible band of MB monomer in water appears normally at
665 nm corresponding to the n* transition of MB (Shahwan et al.,
2011; Rauf et al., 2010; Heger et al., 2005). The relative absorbance
of band at 665 nm is plotted as a function of time to evaluate the
reduction reaction rate (Fig. 7b) in the absence of silver nanoparticles (60 min). The decreasing trend of the absorption intensity
indicates the reduction of MB, but in a slow pace. Increased degradation of MB has been achieved through the inclusion of silver
colloid (sample F1 ) which is shown by a strong decrease in the

Fig. 9. Effect of silver nanoparticles on the degradation of methylene blue to leucomethylene blue. UVvisible absorption spectra of degradation of methylene blue by NaBH4
in the presence of (a) sample F1 (b) sample F3 and(c) sample F5 .

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V.K. Vidhu, D. Philip / Micron 56 (2014) 5462

Fig. 10. Effect of silver nanoparticles on the degradation of eosin Y. UVvisible absorption spectra of degradation of eosin Y by NaBH4 in the presence of (a) sample F1 (b)
sample F3 and(c) sample F5 .

Fig. 11. The rst order linear plot of Ln(A/A0 ) vs. time of (a) methyl orange (b) methylene blue (c) eosin Y for samples F1 , F3 and F5 .

absorption intensity (Fig. 9a). The plot of relative absorption intensity with wavelength in a regular interval of time (1 min) reveals
that the complete reduction of MB to leuco methylene blue (LMB) is
accomplished in less than 20 min in the presence of silver nanoparticles. The size dependent catalytic property has been investigated
for F3 and F5 samples. The catalytic reduction of MB to LMB in the
presence of samples F3 and F5 are shown in Fig. 9b and c, respectively. As compared to the degradation with samples F3 and F5 ,
faster degradation kinetics and higher removal efciencies were
observed for sample F1.
To act as an effective catalyst, the redox potential of silver
nanoparticles needs to be found between the redox potential of
donor (NaBH4 ) and the acceptor (MB) system (Mallick et al., 2011;
Jana et al., 1999). In the present reduction reaction silver nanoparticles exhibit an awesome performance as a catalyst.

4.4.3. Catalytic degradation of eosin Y

Eosin-Y is a tetrabromouorescein (or its disodium salt) dye,
water-soluble, distinctly used in textile and paper industries
(Vignesh et al., 2013). The eosin Y reduction and oxidation reactions
were carefully studied years ago from the one-electron oxidation
and reduction potentials of eosin Y ground state (Santhanalakshmi
and Venkatesan, 2011). Eosin Y (ES2 ) exists as disodium salt and
decolorizes from orange to pale yellow during its reduction to ESH2
(Moser and Graetzel, 1984).
Fig. 7c shows a series of UVvisible absorption spectra of
degradation of eosin Y unsupported by silver nanoparticles. The
reduction reaction rate in the absence of silver nanoparticles is very
slow and took 60 min for the complete degradation. On the addition
of silver nanocatalysts (sample F1 ), the absorbance of dye decreased
quickly with reaction time to almost none within 10 min, which
indicate that the nanocatalysts accelerated the reaction (Fig. 10a).
The effect of size on the reduction reaction has been investigated
by monitoring the catalytic activity of samples F3 (Fig. 10b) and F5
(Fig. 10c). The result emphasize that the catalytic activity has been

improved on the decrease in particle size as in the case of other two

dyes.
The kinetic data obtained for methyl orange, methylene blue and
eosin Y is tted to both rst order and second order rate equations.
Upon analysis, the data emphasizes that the degradation of dyes
seems to follow rst order kinetics (Fig. 11(a) methyl orange, (b)
methylene blue, (c) eosin Y). The rate constants obtained from the
kinetic data for all the three samples is shown in Table 1. The study
on variation in the reaction kinetics based on particle size emphasizes the enhancement of catalytic activity with decrease in particle
size. The degradation of methyl orange, methylene blue and eosin
Y by NaBH4 in the presence of silver nanoparticles is depicted in
Fig. 12.
Catalysis occurs only on the surface of metals, therefore increasing the available surface area will greatly enhance the effectiveness
of the catalyst. Decreasing the particle size will increase the catalytic activity, but there is a critical size below which proves that
further decreases will actually hinder the catalysis (Frelink et al.,
1995).
Metal nanoparticles help in the electron relay from the donor to
the acceptor. The nanoparticles posses a large surface area which
act as a substrate for the electron transfer reaction. Just before the
electron transfer reaction, both of the reactants are adsorbed on the
metal surface. Subsequently, the reactant gains an electron and is
reduced. Thus in all the above catalytic reactions, silver nanoparticles act as an efcient catalyst through the electron transfer process
(Ghosh et al., 2002).
Table 1
Rate constants obtained from kinetic data.
Sample name

F1
F3
F5

First order rate constant (min1 )

Methyl orange

Methylene blue

0.6626
0.2550
0.1931

1.0218
0.7145
0.4877

Eosin Y

0.2312
0.1304
0.0791

V.K. Vidhu, D. Philip / Micron 56 (2014) 5462

61

Fig. 12. The equations depicting degradation of methyl orange, methylene blue and eosin Y to their corresponding products by NaBH4 in the presence of silver nanoparticles.

5. Conclusion
For a healthy future of nanotechnology, green synthetic strategy
should be adopted for nanoparticles synthesis by using environmentally benign and renewable molecules to get rid of hazards
arising out of the use of chemical reducing agents and organic
solvents. Colloid based nanotechnology has been developed to
control nanomaterial size, shape, uniformity and functionality. In
the present article, we have demonstrated the synthesis of silver nanoparticles with varying sizes using T. foenum-graecum seed
extract. The present synthesis method proved to be helpful in
controlling the size of silver nanoparticles, thereby tuning their
catalytic properties. The bioreduced silver nanoparticles exhibited
remarkable size dependent catalytic properties in a reduction reaction of organic dyes, methyl orange, methylene blue and eosin Y.
The utilization of biosynthetic procedure opens new possibilities
for the design of ideal catalyst which exhibits maximum activity
and stability.
Acknowledgements
The authors are pleased to acknowledge NIIST, Thiruvananthapuram, for TEM measurements. Daizy Philip thanks KSCSTE,
Thiruvananthapuram, for nancial assistance.
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