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Materials Today: Proceedings 17 (2019) 568–573 www.materialstoday.com/proceedings

RAMM 2018

Effect of Silver Nitrate Concentration on the Production of Silver

Nanoparticles by Green Method
Y.Z.N. Htwea, W.S. Chowa, Y. Sudab and M. Mariattia*
a
School of Materials and Mineral Resources Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Pulau Pinang,
Malaysia
b
Department of Electrical and Electronic Engineering, Toyohashi University of Technology, Aichi Toyohashi 441-8580, Japan

Abstract

Silver nanoparticles (AgNPs) have been extensively studied for many decades due to their unique features and wide
range of applications. In the present study, AgNPs were synthesized using methanolic leaf extracts from Imperata
cylindrical by green method. Here, effect of silver nitrate (AgNO3) concentrations (0.5 mM, 0.7 mM and 0.9 mM)
on the production of AgNPs was investigated. The synthesized AgNPs were verified by X-ray diffraction (XRD),
UV-visible spectroscopy, scanning electron microscopy (SEM), energy dispersive X-ray (EDX), zeta potential and
surface electrical conductivity. The synthesized AgNPs were consisted of face centered cubic crystals as
demonstrated from XRD studies. Surface plasmon resonance bands of AgNPs occurred in the wavelength range of
417-420 nm. AgNPs exhibit spherical shape and with sizes of 30 to 40 nm. Zeta potential values of AgNPs were -32
to -38 mV. It was found that increased concentration of AgNO3 resulted in increasing crystallite size and size of
AgNPs. Surface electrical conductivity results showed that AgNO3 concentration 0.5 mM produced higher electrical
conductivity 0.435×102 Sm-1 compared to those of 0.7 mM and 0.9 mM concentrations.

© 2019 Elsevier Ltd. All rights reserved.

Selection and peer-review under responsibility of the scientific committee of the 6th International Conference on Recent Advances in Materials,
Minerals & Environment (RAMM) 2018.

Keywords: Silver nanoparticles; imperata cylindrical leaf; electrical conductivity.

* Corresponding author. Tel.: +604-5995262; fax:+604-5996109.

E-mail address: mariatti@usm.my

2214-7853 © 2019 Elsevier Ltd. All rights reserved.

Selection and peer-review under responsibility of the scientific committee of the 6th International Conference on Recent Advances in Materials,
Minerals & Environment (RAMM) 2018.
 Y.Z.N. Htwe et al. / Materials Today: Proceedings 17 (2019) 568–573 569

1. Introduction

Nanotechnology especially nanomaterials have received much consideration because of their structure and
properties differ appreciably from those of molecules, atoms, and bulk materials [1]. Noble metal nanoparticles
(NPs) have been extensively studied for use in applications e.g. optoelectronics, catalysis, sensing and medicine, etc.
[2]. Among various metal nanoparticles, silver nanoparticles (AgNPs) have been widely investigated. Depending on
their size and shapes, AgNPs exhibit unusual optical, electronics and chemical properties, which opens many
possibilities for technological applications.

Generally, AgNPs were prepared by various chemical and physical methods which are quite expensive and
potentially hazardous to the environment. This involves the use of toxic and perilous chemicals that are responsible
for various biological risks [3]. Synthesis of AgNPs using plant extracts as the reducing agents and stabilizers is one
of the most widely used green methods. The source of the plant extract is known to influence the characteristics of
the AgNPs [4]. Table 1 summarizes some of the reports pertaining to AgNPs synthesis mediated by extracts of
various plants used as reducing agent and silver nitrate as a precursor. Jacob et al., [5] reported on the synthesis of
AgNPs using Piper longum leaf extracts. The particles had a uniform spherical shape and ranged in size from18 to
41 nm. Ahamad et al., [6] used extracts of the legume Desmodium triflorum. AgNPs in the size range of 5-20 nm
were produced. Prathna et al., [7] reported the synthesis of AgNPs using an extract of Azadirachta indica leaves and
a solution of silver nitrate. Increasing the reaction time from 30 min to 4h resulted in a progressive increase in the
particle size from around 10 nm to around 35 nm. Patil et al., [8] produced highly stabilized AgNPs with size of (25-
40 nm) using a leaf extract Ocimum tenuiflorum. The particles were antibacterial towards Gram-negative and Gram-
positive bacteria. Krishnaraj et al., [9] synthesized AgNPs (20-30 nm) using a leaf extract of Acalypha indica. The
nanoparticles were shown to be antimicrobial against water borne pathogens such as E.coil and Vibrio cholerae.

Table 1: Green synthesis of silver nanoparticles using plants as reducing agent

Plants Size (nm) References

Piper longum leaf 18 to 41 [6]
Desmodium triflorum 5 to 20 [7]
Azadirachta indica leaves 10 to 35 [8]
Ocimum tenuiflorum leaf 25 to 40 [9]
Acalypha indica 20 to 30 [10]

Imperata (genus) cylindrical (species) Linn, commonly known as dharbai pullu belongs to the kingdom
plante, orderpoales, family poaceae was used as a reducing agent in the present study. It is a perennial rhizomatous
grass native in South East Asia. It grows from 0.6 to 3 m. [10]. In the present study, we focused on the fabrication
and characterization of silver nanoparticles by using green method. The goal of this work is to synthesize AgNPs
using Imperata cylindrical (L) stem as reducing agent. Effect of silver nitrate concentration (0.5 mM, 0.7 mM and
0.9 mM) on the production of AgNPs was investigated.

2. Experimental

2.1 Materials

Fresh Dharbai (Imperata cylindrica) stem and leaves were collected in Universiti Sains Malaysia,
5°08'52.3"N 100°29'27.5"Eand used as a reducing agent. Fig. 1 showed the photograph of Imperata cylindrical.
Silver nitrate (AgNO3) and Ascorbic acid (C6H6O6) were supplied by Merck assay and used as precursor and
surfactant respectively. Ethanol and acetone were supplied by J.T. Baker and were used as cleaning agent. Distilled
water was used in all of the synthesis processes.
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Fig. 1. Imperata cylindrical plant

2.2 Preparation of Imperata cylindrical (L) aqueous extract

Twenty grams of fresh Imperata cylindrical stem and leaves were washed thoroughly with distilled water
and shade-dried for 2 days and finely powdered. 10 grams of powdered sample was boiled with 100 ml of distilled
water at 60°C for 20 minutes, filter and made up to 100 ml.

2.3 Synthesis of silver nanoparticles (AgNPs)

In this study, silver nitrate (AgNO3) was used as a precursor while Imperata cylindrical (L) stem and
ascorbic acid (C6H8O6) were used as the reducing agent and surfactant, respectively. The concentration of AgNO3
was varied by 0.5 mM, 0.7 mM, and 0.9 mM in order to observe the effect of these parameters especially on the size
and morphology of the AgNPs produced. 80 ml of AgNO3 was first heated to 60°C and was then added (with
vigorous stirring) to 20 ml of an Imperata cylindrical aqueous extract and ascorbic acid solution that was preheated
to 60°C. The mixture was then stirred for 20 minutes. After that, the heating was stopped and the solution was
cooled at room temperature with continuous stirring. The precipitates of AgNPs then were collected using
centrifugation process due to the incapability of the nanoparticles to sediment spontaneously after the reaction
process. This precipitates of AgNPs then washed by acetone and ethanol using vacuum filtration. The powder was
obtained after drying in a vacuum oven at 80°C. Fig. 2 shows a schematic diagram of the synthesis process.The
AgNPs particles were pressed using pressing machine to form a pellet for electrical conductivity measurement.

Fig. 2. Schematic diagram of silver nanoparticles

2.4 Material Characterization

X-ray diffraction XRD patterns were obtained using a Bruker D8 X-ray diffractometer with a Ni-filtered
Cu-Kα (λ = 1.54021Å) radiation source and were used to identify the crystallographic structure of the AgNPs. The
morphology of the as-produced AgNPs was analysed using field emission scanning electron microscopy (FESEM,
model Zeiss Supra 35VP). Ultraviolet-visible Spectroscopy (UV-vis) was performed in a Perkin-Elmer 35
spectrophotometer. The zeta potential of AgNPs was measured using a Malvern Nano series ZEN3600. The surface
electrical conductivity of the AgNPs was measured using a Prostat PRS-812 resistance meter measurement system.
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3. Results and discussion

The crystal structure and the formation of silver nanoparticles were analysed by X-ray diffraction (XRD).
Fig. 3 shows XRD patterns of silver nanoparticles produced using a different concentration of AgNO3 0.5 mM, 0.7
mM, and 0.9 mM respectively. By using JCPDS database, there are five characteristic peaks corresponding to Miller
indices (111), (200), (220), (311) and (222), detected at 38°, 44°, 64°, 77° and 82° respectively, which can be
indexed according to the facets of the face centred cubic crystal structure of silver [11]. In detail, Table 2 records the
crystallite sizes and particle sizes obtained from XRD and FESEM analysis. From that, the synthesis portrayed that
the average crystallite sizes of the synthesized AgNPs showed the parallel progression of increasing values with the
average sizes collected from its respective FESEM observations in Fig.s 4. Here, as the concentrations of silver
nitrate increased from 0.5 mM to 0.7 mM and 0.9 mM, the average crystallite sizes of the AgNPs have increased
from 23.87 nm to 24.51 nm and 25.16 nm, respectively. This result is consistent with previous work by Ajitha et al.,
[12] and Janardhanan et al., [13]. They reported a direct relationship between the initial concentrations of metal ions
with the average nanoparticle size where increasing of initial concentration of metal ions results in increased size of
nanoparticles produced.

Fig 3. XRD pattern ( of AgNPs prepared at different concentration of AgNO3, (a) 0.5 mM (b) 0.7 mM (c) 0.9 mM

Table 2: XRD crystallite sizes of AgNPs and SEM size distributions of the synthesized AgNPs with increasing concentrations of AgNO3.

AgNO3 concentration Crystallite sizes (nm) Particles sizes (nm)

0.5 mM 23.87 32.70

0.7 mm 24.51 37.24

0.9 mM 25.16 39.91

Fig. 4 shows the FESEM images of silver nanoparticles prepared at different concentrations of AgNO3 All
samples show similar morphology which is the quasi-spherical shape. The average particle size of AgNPs
nanoparticles were masured using Image J software. Based on the measurement, it can be observed that the average
particle size of silver nanoparticles increased from 32.70 nm, 37.24 nm, 39.91 nm at 0.5 mM, 0.7 mM, and 0.9 mM
concentration of silver nitrate, respectively. Previous works by Goh et al., [14] and Bicer and Sisman [15] reported
similar observation that smaller particles could be generated by decreasing the concentration of metal salt used.
Theoretically, the reaction conversion rate ions to the metal particle are dependent on the initial concentration of
metal ions [16].
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Fig. 4. FESEM micrograph of AgNPs as a function of AgNO3 concentrations; (a) 0.5 mM, (b) 0.7 mM and (c) 0.9 mM at
magnifications of 20 KX

Fig. 5 shows the UV-Vis spectra of the AgNPs with increasing concentrations of silver nitrate. The
similarities showed by the emergence of a single SPR band in all samples indicated that the AgNPs were isotropic in
nature. Fig. 5 shows that the absorption peak at 0.5 mM was narrower than samples at 0.7 mM and 0.9 mM.
According to Song et al., [17], the narrower absorption peak implies a better degree of nanoparticles distribution.
The absorption of silver nanoparticles at 0.5 mM also shows the occurrence of the peak at approximately 417 nm
and this peak slightly changed to 424 nm at 0.7 mM and 0.9 mM of silver nitrate. This redshift (417 nm to 424 nm)
indicated the increasing particle size of silver nanoparticles that also proved by FESEM images in Fig. 4.

Fig. 5. UV-vis spectrum of AgNPs as a function of silver nitrate concentrations

Zeta potential analysis was used to determine the stability of AgNPs. Table 3 shows zeta potential values
and electrical conductivity values of the AgNPs with increasing concentrations of silver nitrate. Nanoparticles with
zeta potential values greater than +30 mV or less than -30 mV typically exhibit high degrees of stability because of
the inter-particle electrostatic repulsion [18]. Here, as the concentrations of silver nitrate increases from 0.5 mM to
0.7 mM and 0.9 mM, the zeta potential values of AgNPs have increased from 25.87 nm to 24.51 nm and 23.16 nm,
respectively. Based on Table 3, it was found that the electrical conductivity values of AgNPs decreased with
increasing concentration of AgNO3. Addition of less AgNO3 produced small size of AgNPs, (refer to Table 2). This
is related high surface area per unit volume shown by small AgNO3 particles and this subsquently increase the
particle connectivity and increase electrical conductivity.
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Table 3: Zeta potential and electrical conductivity results of the synthesized AgNPs with increasing concentrations of AgNO3

AgNO3 concentration Zeta potential Electrical conductivity (Sm-1)

0.5 mM -38 39.91

0.7 mm -35 37.24

0.9 mM -32 32.91

4. Conclusions

The study demonstrated that AgNPs can be synthesized using (Imperata cylindrical) plant extract, as a
reducing agent by using green method.. The green method proved to be environmental friendly and effective
approach to synthesize of AgNPs. The X-ray diffraction and UV-vis spectroscopy confirmed the formation of silver
nanoparticles. XRD and FESEM analysis showed the increase of crystallite sizes and particles sizes with increasing
silver nitrate concentration. Zeta potential values which were less than -30 mV indicate the stability of the
nanoparticles. Electrical conductivity values of synthesized AgNPs decreased with increasing AgNO3
concentrations.

Acknowledgements

The authors gratefully acknowledge ASEAN University Network for Science and Engineering Education
Development Network (AUN/SEED-Net) Project and Japan International Cooperation Agency (JICA) and Malaysia
Government (FRGS grant 6071385) for their financial support. They would also like to thank the Universiti Sains
Malaysia (USM) and the School of Materials and Mineral Resources Engineering for the use of their facilities.

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