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org/Langmuir
© 2010 American Chemical Society

Biosynthesis of Iron and Silver Nanoparticles at Room Temperature

Using Aqueous Sorghum Bran Extracts
Eric C. Njagi,† Hui Huang,† Lisa Stafford,† Homer Genuino,† Hugo M. Galindo,† John B. Collins,‡
George E. Hoag,‡ and Steven L. Suib*,†,§
†
Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269-3060, United States,
‡
VeruTEK Technologies, Inc., 65 West Dudley Town Rd, Suite 100, Bloomfield, Connecticut 06002,
United States, and §Department of Chemical Engineering, and Institute of Materials Science, University of
Connecticut, U-3060, 55 North Eagleville Rd., Storrs, Connecticut 06269-3060, United States

Received August 11, 2010. Revised Manuscript Received November 22, 2010

Iron and silver nanoparticles were synthesized using a rapid, single step, and completely green biosynthetic method
employing aqueous sorghum extracts as both the reducing and capping agent. Silver ions were rapidly reduced by the
aqueous sorghum bran extracts, leading to the formation of highly crystalline silver nanoparticles with an average
diameter of 10 nm. The diffraction peaks were indexed to the face-centered cubic (fcc) phase of silver. The absorption
spectra of colloidal silver nanoparticles showed a surface plasmon resonance (SPR) peak centered at a wavelength of 390 nm.
Amorphous iron nanoparticles with an average diameter of 50 nm were formed instantaneously under ambient
conditions. The reactivity of iron nanoparticles was tested by the H2O2-catalyzed degradation of bromothymol blue as
a model organic contaminant.

1. Introduction methods. Consequently, nanomaterials have been synthesized

Metallic nanoparticles have attracted tremendous interest due
to their unique optoelectronic and physicochemical properties.
Their applications include use in biosensing,1 media recording,2
optics,3 catalysis,4 and environmental remediation.5-10
Metallic nanoparticles of specific sizes and morphologies can
be readily synthesized using chemical and physical methods.11-15
However, these methods employ toxic chemicals as reducing
agents, organic solvents, or nonbiodegradable stabilizing agents
and are therefore potentially dangerous to the environment and
biological systems.16 Moreover, most of these methods entail intricate
controls or nonstandard conditions making them quite expensive.
The biosynthesis of nanoparticles has been proposed as a cost-
effective environmental friendly alternative to chemical and physical
using microorganisms17-21 and plant extracts.22-28 The use of plant
extracts for synthesis of nanoparticles is potentially advantageous
over microorganisms due to the ease of scale up, the biohazards,
and elaborate process of maintaining cell cultures.24,29,30 Gold
and silver nanoparticles have been synthesized using various plant
extracts including hibiscus (Hibiscus rosa sinensis) leaf extract,31
neem (Azadirachta indica) leaf broth,23 black tea leaf extracts,32
Indian gooseberry (Emblica officinalis) fruit extract,24 sundried
camphor (Cinnamomum camphora) leaves,33 and Aloe vera plant
extract.25 The biosynthesis of iron oxides and antimony trioxide
(Sb2O3) using plant extracts has also been reported.20,34
Recently, silver and iron nanoparticles of various sizes and
morphologies have been synthesized using coffee and green tea

*Corresponding author. E-mail: steven.suib@uconn.edu.
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264 DOI: 10.1021/la103190n Published on Web 12/06/2010 Langmuir 2011, 27(1), 264–271
Njagi et al.
extracts.26-28 Stable polydispersed spherical silver nanoparticles
with sizes ranging from 5 to 100 nm were obtained using aqueous
coffee and tea extracts.26 Iron nanoparticles of various sizes
and morphologies (spherical, platelets, and nanorods) were also
formed instantaneously using aqueous tea extracts.27,28 The size
and crystallinity (hexagonal metallic iron, amorphous iron, and
R-Fe2O3) of the synthesized iron nanoparticles were found to
depend on the concentration of the tea extract in the reaction
mixture.27 The synthesized iron nanoparticles were found to be
nontoxic when compared with iron nanoparticles prepared using
conventional NaBH4 reduction protocols.27 The synthesized iron
nanoparticles also effectively catalyzed the H2O2 degradation
of bromothymol blue, a model compound for environmental
remediation.28 The iron nanoparticles were effectively capped by
the tea polyphenols, extending their lifetime.
Although the synthesis of metallic nanoparticles using plant
materials has been demonstrated, a rapid, cost-effective biosyn-
thetic protocol for bulk synthesis of stable metallic nanoparticles
has not been developed. Such a method is important for the full
potential of these nanomaterials in environmental remediation
and other technological applications to be realized. Most biological
methods reported in the literature use dilute (e10-3 M) metal ion
solutions forming low concentrations of colloids.23-25,31,34
In this study, we report the biosynthesis of iron and silver
nanoparticles via a single-step, room-temperature reduction of
iron and silver ions using aqueous hybrid sorghum (Sorghum spp)
bran extracts. The reduction of the metal ions using aqueous
sorghum bran extracts is rapid and results in moderately stable
colloids. Specialty sorghums contain high levels of diverse phe-
nolic compounds that can function as both reducing and capping
agents in the synthesis of metallic and metal oxide nanoparticles.
These phenolic compounds are water-soluble, nontoxic, and bio-
degradable, affording a green synthesis process.
Specialty hybrid sorghums with high levels of freely extractable
phenolic compounds are potentially more cost-effective and
advantageous than the use of coffee and tea for bulk synthesis
of metallic nanoparticles. Most sorghum varieties are drought
and heat tolerant, making sorghum economical to produce.35 On
the contrary, the production of coffee and tea requires very
specific climatic conditions, longer maturity times, and expensive
processing.36,37 Further, sorghum bran is primarily used as a
feedstock and for production of alcohol and other industrial
products while coffee and tea are commonly used as behavioral
stimulants and for other therapeutic uses.28,35
The performance of the synthesized iron nanoparticles in the
degradation of organic contaminants was investigated using bromo-
thymol blue (BTB) as a model organic contaminant. BTB is a useful
probe molecule for free radical oxidation that is easily monitored
using UV-vis spectroscopy due to its concentration-dependent
absorption in the visible region. BTB has been used as a model
compound to study TiO2-mediated photocatalytic degradation
treatment of wastewater contaminated with dye effluents.38
Bromothymol blue has also been used as a probe compound to
study the effects of microwave irradiation and auxiliary oxidants
(ozone and UV) on TiO2-assisted photodegradation of organic
contaminants in water.39 BTB is a useful probe molecule that can
only be chemically degraded via free-radical pathways unlike
methylene blue, which undergoes direct oxidation by persulfate.28
(35) Awika, J. M.; Rooney, L. W. Phytochemistry 2004, 65, 1199–1221.
(36) DaMatta, F. M.; Ramalho, J. D. C. Braz. J. Plant Physiol. 2006, 18, 55–81.
(37) Carr, M. K. V. Exp. Agric. 1972, 8, 1–14.
(38) Haque, M. M.; Muneer, M. Dyes Pigm. 2007, 75, 443–448.
(39) Park, S. H.; Kim, S.; Seo, S.; Jung, S. Nanoscale Res. Lett. 2010, 5, 1627–
1632.
Langmuir 2011, 27(1), 264–271
Article
2. Experimental Methods
2.1. Materials and Chemicals. Iron(III) chloride hexahydrate
(FeCl3 3 6H2O, Fluka; >98%), bromothymol blue (Sigma-Aldrich;
ACS reagent), gallic acid (Sigma-Aldrich, 97.5-102.5%), sodium
carbonate (Sigma-Aldrich, >99.0%), Folin-Ciocalteu’s phenol
reagent (Sigma-Aldrich, 2 N), hydrogen peroxide (H2O2, Fisher
Scientific; 30% solution), and silver nitrate (AgNO3, Alfa Aesar;
99.9%) were used in this study without further purification. All
aqueous solutions were made using distilled deionized water (DDW).
Specialty sorghum bran (Sorghum spp) powder was obtained
from VeruTEK Technologies Inc. (Bloomfield, CT). Sorghum
bran extracts are rich in polyphenols, policosanols, and other
reductive biomolecules containing multiple hydroxyl functional
groups such as flavonoids and phenolic acids.35,40 These phenolic
compounds have reduction potential values ranging from 0.3 to
0.8 V and are mainly responsible for bioreduction of metal ions
and stabilization of the resultant nanoparticles.27,28
2.2. Preparation of Iron and Silver Nanostructures. Sorghum
bran powder (8.3 g) was extracted with 125 mL of DDW at 25, 50,
and 80 °C while being continuously stirred for 30 min. After
extraction, samples were centrifuged at 8000 rpm for 30 min. The
resultant supernatant was collected, filtered, and stored at -20 °C
before use. The total phenolic content of the aqueous sorghum
bran extracts was determined by the Folin-Ciocalteu method
using gallic acid as a standard phenolic compound as described
by Slinkard and Singleton.41 Absorbance was measured at 765 nm
using a Jasco V530 UV-vis spectrophotometer, and results were
expressed as mg/L gallic acid equivalent (GAE). The total phenolic
content of the extracts was 2010, 2375, and 2520 mg/L GAE for
sorghum bran extracted at 25, 50, and 80 °C, respectively. This
indicates that the extraction efficiency increased with increase of
extraction temperature. The pH values of the aqueous sorghum
extracts were 6.30, 6.12, and 5.86 for sorghum extracted at 25, 50,
and 80 °C, respectively.
Iron nanoparticles were prepared by adding 0.1 M FeCl3
solution to the sorghum bran extract (supernatant at ambient
temperature) in a 2:1 volume ratio. The mixture was hand shaken
for 1 min and allowed to stand at room temperature for 1 h. The
same procedure was used to synthesize silver nanoparticles using
0.1 M AgNO3 solution.
2.3. Characterization of Nanoparticles. Morphological
studies were performed using field emission scanning electron
microscopy (FE-SEM) and high-resolution transmission electron
microscopy (HR-TEM).
The FE-SEM micrographs were obtained using a JEOL 6335F
FE-SEM microscope equipped with a Thermo Noran energy
dispersive spectroscopy (EDS) detector. The HR-TEM images
were obtained using a JEOL 2010 FasTEM microscope equipped
with an energy dispersive spectroscopy (EDS) detector. The
powder X-ray diffraction (XRD) patterns were recorded using a
Scintag 2000 PDS diffractometer with Cu KR radiation, a beam
voltage of 45 kV, and current of 40 mA. The UV-vis absorption
spectra were obtained using a Jasco V530 UV-vis spectrophotom-
eter. The elemental analysis of the samples was performed using
energy dispersive spectroscopy (EDS). The zeta (ζ) potential
measurements were carried out using a Zetasizer Nano ZS 90
(Malvern Instruments).
2.4. Degradation of Bromothymol Blue. The bromothy-
mol blue solution (500 mg/L) was prepared by dissolving 50 mg of
bromothymol blue in 100 mL of DDW. Blanks were prepared by
adding 7.3, 15, and 30 μL of the colloidal iron nanoparticles to
3 mL of DDW to make solutions with iron concentrations of
0.16, 0.33, and 0.66 mM, respectively. Samples were prepared by
mixing 3 mL of the 500 mg/L (0.8 mM) bromothymol blue and
200 μL of 30% H2O2 (0.68 M) in a cuvette. The cuvette was then
(40) Hahn, D. H.; Faubion, J. M.; Rooney, L. W. Cereal Chem. 1983, 60,
255–259.
(41) Slinkard, K.; Singleton, V. L. Am. J. Enol. Vitic. 1977, 28, 49–55.
DOI: 10.1021/la103190n 265
Article Njagi et al.

Figure 1. XRD patterns of silver nanoparticles synthesized using sorghum bran extracted at 25, 50, and 80 °C.

Figure 2. UV-vis spectra of colloidal silver nanoparticles synthesized using sorghum bran extracted at (a) 25, (b) 50, and (c) 80 °C.
inserted in the spectrophotometer, and the iron nanoparticles
were added to the solution and quickly mixed with a pipet. Scans
were started immediately after the addition of iron, and the solution
was left untouched until completion. Absorbance was monitored
at the wavelength of maximum absorption (λmax = 431 nm).
3. Results
3.1. Preparation of Silver Nanoparticles. Metallic silver
nanoparticles formed within a few minutes at room temperature
when silver nitrate solution was added to the aqueous sorghum
extracts. The solutions turned yellow-brown, indicating the for-
mation of silver nanoparticles, which absorb radiation in the
visible region (ca. 380-450 nm).42 The pH values of the colloidal
silver nanoparticles synthesized using sorghum extracted at 25,
50, and 80 °C were 3.46, 3.45, and 3.44, respectively.
3.1.1. Crystallographic Structures. The XRD patterns of
synthesized silver nanoparticles are shown in Figure 1. The nano-
particles are highly crystalline with diffraction peaks corresponding
(42) Huang, H.; Yang, X. Carbohydr. Res. 2004, 339, 2627–2631.

266 DOI: 10.1021/la103190n Langmuir 2011, 27(1), 264–271

Njagi et al. Article

Figure 3. FE-SEM images of silver nanoparticles prepared using

sorghum bran extracted at (a) 25, (b) 50, and (c) 80 °C.

to the face-centered cubic (fcc) phase of metallic silver. The cal-

culated lattice constant (a = 4.0602 Å) is in good agreement with
the reported value (JCPDS 4-783; a = 4.0862 Å). The patterns
lack diffraction peaks corresponding to impurities or oxides Figure 4. TEM images of silver nanoparticles synthesized using
except for a broad bump about 2θ=25° most likely from organic sorghum bran extracted at (a) 25, (b) 50, and (c) 80 °C.
moieties present in the extracts.16,33
3.1.2. UV-vis Absorption. The UV-vis spectra of diluted
(10) colloidal silver nanoparticles are shown in Figure 2. An
intense surface plasmon resonance (SPR) peak is observed at
390 nm. All spectra presented a minimum at ∼320 nm. Colloidal
silver nanoparticles synthesized using the sorghum bran extracted
at 80 °C had the most intense SPR peak, suggesting a higher
number of absorbing particles, attributable to increased extrac-
tion efficiency with temperature.
3.1.3. Morphology of Silver Nanoparticles. Figure 3 shows
the FE-SEM images of silver nanostructures synthesized using
the sorghum extracts. The nanoparticles appear to aggregate and
form nanoclusters inside the extract matrix. However, these
nanoclusters are well separated from each other. The nanoparti-
cles are largely uniform with a narrow size distribution. The high-
resolution transmission electron microscope (HR-TEM) micro-
graphs (Figure 4) show that the silver nanoparticles are spherical
with an average diameter of about 10 nm.
3.1.4. Composition of Silver Nanoparticles. The elemental
Figure 5. EDS spectrum of silver nanoparticles prepared using
composition of powdered samples was determined using FE- sorghum bran extracted at 80 °C.
SEM equipped with an EDS detector. Figure 5 shows a repre-
sentative EDS spectrum of the synthesized silver nanoparticles. are amorphous. In the XRD patterns of silver, broad humps are
The spectrum shows the nanoparticles are primarily composed of present at about 2θ = 25°, which can be attributed to organic
silver with the only noticeable contaminant being phosphorus materials in the matrix.
presumably from the sorghum extract. 3.2.2. UV-vis Absorption. The UV-vis spectra of the iron
3.2. Preparation of Iron Nanoparticles. On adding ferric nanoparticles are shown in Figure 7. There is continuous absorp-
chloride solution to the aqueous sorghum extracts, the solutions tion in the visible range. Nadagouda et al.27 obtained similar
instantaneously turned from pale yellow to dark brownish, UV-vis spectra for amorphous iron nanoparticles synthesized
indicating the formation of iron nanoparticles.27 The pH values using tea polyphenols. Colloidal samples prepared with sorghum
of iron nanoparticles prepared using sorghum extracted at 25, 50, extracted at 25 and 80 °C had the least and most absorbance in the
and 80 °C were 2.24, 2.20, and 2.10, respectively. The as-synthesized whole visible range, respectively.
colloidal iron nanoparticles had ζ potentials of 14.6, 13.3, and 3.2.3. Morphology of Iron Nanoparticles. The FE-SEM
11.4 for samples prepared using sorghum extracted at 25, 50, and images of iron nanoparticles are shown in Figure 8. These images
80 °C, respectively. Sedimentation was not observed after a week suggest that the particles agglomerate to form irregular clusters.
of storage. This suggests that the synthesized iron nanoparticles The average diameter of the iron nanoparticles calculated from
were stabilized by the polyphenols in the sorghum extracts. HR-TEM micrographs (Figure 9) is about 50 nm. The selected
3.2.1. Crystallographic Structures. The XRD patterns of area electron diffraction (SAED) micrographs (insets of Figure 9)
iron nanoparticles are shown in Figure 6. The patterns lack have no diffraction rings or spot patterns but show a diffuse ring,
distinct diffraction peaks, suggesting that the iron nanoparticles confirming the amorphous nature of the iron nanoparticles.

Langmuir 2011, 27(1), 264–271 DOI: 10.1021/la103190n 267

Article
Figure 6. XRD patterns of iron nanoparticles synthesized using sorghum bran extracted at 25, 50, and 80 °C.
3.2.4. Elemental Composition. Figure 10 shows a representa-
tive EDS spectrum of the iron nanoparticles. The iron nano-
particles are primarily composed of iron. The spectrum also reveals
the presence of residual chloride ions and phosphorus impurities.
Oxygen is also present suggesting surface oxidation of the iron
nanoparticles.
3.2.5. Catalytic Studies. Figure 11 shows the degradation of
bromothymol blue with time using 2% hydrogen peroxide and
various concentrations of the synthesized iron nanoparticles.
The initial concentration of bromothymol blue was 500 mg/L.
Degradation of bromothymol blue did not occur in the presence
of only 2% H2O2, indicating there was no direct oxidation pathway
by peroxide. However, degradation of BTB occurred in the presence
of 2% H2O2 and iron nanoparticles, suggesting degradation via
free radical pathways. The degradation of BTB was fastest in the
presence of 2% H2O2 and 0.66 mM iron nanoparticles leading to
a 90% decrease in the concentration of BTB within 30 min. In
the presence of 2% H2O2 and 0.33 mM iron nanoparticles about
60% of BTB was degraded in 30 min. The degradation was signif-
icantly slower in the presence of 2% H2O2 and 0.16 mM iron
nanoparticles with only about 20% BTB being degraded after
30 min. Thus, these results indicate that higher iron concentrations
accelerated the degradation of bromothymol blue.
4. Discussion
When AgNO3 solution was added to the sorghum extract, the
solution immediately turned from pale yellow to yellow-brownish,
indicating the formation of silver nanoparticles.42 The yellowish-
brownish color results from absorption by colloidal silver nano-
particles in the visible (380-450 nm) region of the electromagnetic
spectrum due to the excitation of surface plasmon vibrations.42,43
The ultraviolet-visible absorption spectra of colloidal silver
nanoparticles exhibited characteristic surface plasmon resonance
(SPR) bands centered at 390 nm. The location of the SPR peak on
(43) Ahmad, A.; Mukherjee, P.; Senapati, S.; Mandal, D.; Khan, M. I.; Kumar,
R.; Sastry, M. Colloids Surf., B 2003, 28, 313–318.
268 DOI: 10.1021/la103190n
Njagi et al.
the lower end of the absorption range (380-450 nm) indicates
that the colloidal dispersion was primarily composed of small
spherical silver nanoparticles.44,45 The small sizes (∼10 nm) and
the spherical nature of the silver nanoparticles were confirmed by
our TEM results.
All spectra presented a minimum at ∼320 nm that corresponds
to the wavelength at which the real and imaginary parts of the
dielectric function of silver almost vanish.46 The plasmon bands
are broad with an absorption tail in the longer wavelengths due to
the size distribution of the particles.47 Similar UV-vis spectra
were obtained for silver nanoparticles prepared using hibiscus
(Hibiscus rosa sinensis) leaf extract and neem (Azadirachta indica)
leaf broth.23,31 The intensity of the absorption bands increased
with the temperature of extraction of the sorghum bran, suggest-
ing an increase in the concentration of silver nanoparticles. This is
in agreement with our phenolic content values that increased with
extraction temperature, which suggests that phenolic compounds
are the principal reducing agents.
The synthesized silver nanoparticles were highly crystalline
with diffraction peaks corresponding to the face-centered cubic
(fcc) phase of metallic silver. The five diffraction peaks present in
the spectra at 2θ values of 38.35°, 44.49°, 64.68°, 77.58°, and 81.66°
were indexed to the (111), (200), (220), (311), and (222) reflections
of the fcc structure of metallic silver. No extra diffraction peaks
were present, suggesting that the synthesized silver was essentially
pure. The high purity and the low toxicity of aqueous sorghum
extracts render the synthesized silver nanoparticles potentially
attractive for biological applications. Morphological studies using
FE-SEM showed that silver nanoparticles formed nanoclusters
inside the extracts. HR-TEM showed these spherical nanoparticles
(44) Creighton, J. A.; Eadon, D. G. J. Chem. Soc., Faraday Trans. 1991, 87,
3881–3891.
(45) Petit, C.; Lixon, P.; Pileni, M. J. Phys. Chem. 1993, 97, 12974–12983.
(46) Elechiguerra, J. L.; Burt, J. L.; Morones, J. R.; Camacho-Bragado, A.;
Gao, X.; Lara, H. H.; Yacaman, M. J. J. Nanobiotechnol. 2005, 3, 6.
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Paralikar, K. M.; Balasubramanya, R. H. Mater. Lett. 2007, 61, 1413–1418.
Langmuir 2011, 27(1), 264–271
Njagi et al.
Figure 7. UV-vis spectra of colloidal iron nanoparticles prepared using sorghum bran extracted at (a) 25, (b) 50, and (c) 80 °C.
Figure 8. FE-SEM images of iron nanoparticles synthesized using
sorghum bran extracted at (a) 25, (b) 50, and (c) 80 °C.
are largely uniform with an average diameter of about 10 nm,
which is within the size range critical for their biological appli-
cations.44 HR-TEM results reveal the size of silver nanoparticles
prepared using sorghum extracted at 50 °C is smaller compared to
the size of silver nanoparticles prepared using sorghum extracted
at 25 and 80 °C. Nadagouda et al.27 observed that the concentra-
tion of phenolic compounds is critical to the size and morphology
of metallic nanoparticles. Thus, the concentration of phenolic
compounds in the sorghum extracts might be the key determinant
of the size of the resultant nanoparticles.
The UV-vis spectra of iron nanoparticles synthesized using
aqueous sorghum extracts showed continuous absorption in the
visible range. Nadagouda et al.27 obtained similar UV-vis spectra
for amorphous iron nanoparticles synthesized using aqueous tea
extracts. The powder XRD patterns of iron nanoparticles did not
have distinct diffraction peaks, suggesting that the synthesized
iron nanoparticles were amorphous. The amorphous nature of
Langmuir 2011, 27(1), 264–271
Article
Figure 9. TEM images of iron nanoparticles synthesized using
sorghum bran extracted at (a) 25, (b) 50, and (c) 80 °C.
the iron nanoparticles was confirmed by the SAED analysis. The
HR-TEM micrographs show that the iron nanoparticles are well
separated from each other, suggesting effective capping by water-
soluble heterocyclics present in the sorghum extracts.
The HR-TEM results also revealed that the iron nanoparticles
synthesized using sorghum extracts were spherical with sizes
ranging from 40 to 50 nm. Nadagouda and co-workers27 have
synthesized iron nanoparticles of different sizes and morphologies
using aqueous tea extract. The sizes and morphologies of the
synthesized iron nanoparticles were found to be dependent on the
DOI: 10.1021/la103190n 269
Article Njagi et al.

Figure 10. EDS spectrum of iron nanoparticles prepared using sorghum bran extracted at 80 °C.

Figure 11. Degradation of BTB over time with iron nanoparticles catalyzed H2O2: (a) control (BTB with 2% hydrogen peroxide (HP)
solution); (b) BTB treated with 0.16 mM (as Fe) iron nanoparticles and 2% HP; (c) BTB treated with 0.33 mM (as Fe) iron nanoparticles and
2% HP; (d) BTB treated with 0.66 mM (as Fe) iron nanoparticles and 2% HP.

concentration of the tea extract. Elemental analysis using EDS
revealed the presence of oxygen in the synthesized iron nanopar-
ticles. Metallic iron nanoparticles often react spontaneously upon
exposure to air or water to form iron-iron oxide core-shell
nanoparticles.48,49 The pH of the synthesized iron colloids was
about 2, suggesting that amorphous iron oxyhydroxide, which is
known to form at low pH, might have precipitated.50 Magnetic
and spectroscopic experiments are ongoing to determine the
composition of the synthesis iron nanoparticles. The EDS results
also revealed the presence of phosphorus in the synthesized silver
and iron nanoparticles. Phosphorus is vital to plant growth and is
found in every living plant cell. Phosphorus ions are known to
adsorb on nanoparticles (especially on iron oxyhydroxides) at low
(48) Li, X.; Elliott, D. W.; Zhang, W. Crit. Rev. Solid State Mater. Sci. 2006, 31,
111–122.
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pH, which would explain the presence of phosphorus in the
synthesized nanoparticles.51
Iron nanoparticles are increasingly being utilized in environ-
mental remediation and hazardous waste treatment. However, these
nanoparticles exhibits a strong tendency to aggregate leading to
rapid sedimentation and limited mobility especially in aquatic
environments. Nonstabilized iron nanoparticles are known to
settle out of solution in less than 10 min.52 This has limited the use
of iron nanoparticles in environmental remediation. The zeta (ζ)
potential is commonly used to assess the stability of colloidal
systems.52,53 Colloidal systems with ζ potentials greater than
(30 mV are normally considered stable.52 The as-synthesized
colloidal iron nanoparticles had ζ potentials of 14.6, 13.3, and
11.4 for samples prepared using sorghum bran extracted at 25, 50,
(51) Antelo, J.; Avena, M.; Fiol, S.; Lopez, R.; Arce, F. J. Colloid Interface Sci.
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270 DOI: 10.1021/la103190n Langmuir 2011, 27(1), 264–271

Njagi et al.
and 80 °C, respectively. The magnitude of ζ potentials of the
as-synthesized colloidal systems implies an incipient instability
with iron nanoparticles in the dispersion bound to aggregates in
the long run. However, no noticeable flocculation or sedimentation
was observed after storage for a week, suggesting the sorghum
extract was able to stabilize the nanoparticles to some extent.
This can be attributed to steric stabilization by polyphenols and
other water-soluble heterocyclics present in the aqueous sorghum
extracts.35,54 This level of stabilization is potentially useful for
environmental and electrocatalytic applications where preventing
aggregation while providing accessibility to the nanoparticles
is vital.14
Iron nanomaterials are very efficient at removing organic con-
taminants, organic matter (e.g., humic and fulvic acids), and arsenic
from ground waters due to their large surface areas, high surface
reactivity, and high sorption capacity.55-61 The reactivity of the
synthesized iron nanoparticles was tested using bromothymol
blue, a useful probe molecule that does not undergo direct oxidation
by H2O2 but degrades via free-radical pathways.28 Bromothymol
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Langmuir 2011, 27(1), 264–271
Article
blue degrades rapidly in the presence of iron nanoparticles and
H2O2, indicating that the iron nanoparticles act as catalysts for
free radical production from H2O2. The catalysis of H2O2
increases with increasing concentrations of iron nanoparticles,
leading to increase in the rate of degradation of bromothymol
blue. These results suggest that iron nanoparticles synthesized
using aqueous sorghum extracts are potentially useful for degra-
dation of organic pollutants.
5. Conclusions
The synthesis of iron and silver nanoparticles using aqueous
sorghum bran extracts has been demonstrated. These nanoparti-
cles were prepared at ambient conditions with sorghum poly-
phenols acting as both the reducing and stabilizing agents. Highly
crystalline spherical metallic silver nanoparticles of about 10 nm
were prepared. These silver nanoparticles were of high purity,
making them potentially useful for biological applications. The
synthesized iron nanoparticles effectively catalyzed H2O2 degra-
dation of a model organic compound, making them potentially
useful for environmental remediation and treatment of hazardous
waste. This biological method is potentially attractive for large-
scale synthesis of metallic and metal oxide nanomaterials.
Acknowledgment. We acknowledge financial support from
VeruTEK Technologies Inc. and the Department of Energy, Office
of Basic Energy Sciences, Division of Geochemical, Biological
and Chemical Sciences. The authors also thank Dr. Lichun Zhang
for assisting with microscopy experiments and Dr. Raymond Joesten
for helpful suggestions. We also thank Aimee Morey-Oppenheim
for performing preliminary magnetic measurements.
DOI: 10.1021/la103190n 271