Proceedings of IWNA 2013, 14-16 November 2013, Vung Tau, Vietnam

NMD-089-P

SYNTHESIS AND STABILITY CONTROL OF SILVER NANOPARTICLES

PREPARED BY USING GLUCOSE AS CAPPING AGENT IN CHEMICAL
REDUCTION METHOD
Chinh Dung Trinh, Dung My Thi Dang, Thanh Nu Thi Le, Thuy Thi Le, Chien Mau Dang
Laboratory for Nanotechnology, Vietnam National University, Ho Chi Minh City, Community 6, Linh Trung
Ward, Thu Duc District, Ho Chi Minh City, Vietnam;
Email: tdchinh@vnuhcm.edu.vn

ABSTRACT
Proceedings of IWNA 2013, 14-16 November 2013, Vung Tau, Vietnam

In this work, we investigate a simple chemical reduction method is used to prepare silver
nanoparticles. We use glucose (C6H12O6) which was oxidized to form gluconic acid as stabilizer
and capping agents. Triethanolamine (C 6H15NO3) was used as the main reducing agent and a
catalyst in order to oxidize glucose to form gluconic acid. The obtained silver nanoparticles were
characterized by, transmission electron microscopy (TEM) and UV-visible spectrophotometry
(UV-vis). The main purpose of this paper is to report a simple method synthesize silver
nanoparticles using glucose as capping agents which have smaller molecular weight than
common capping agents have large molecular weight such as polyvinylpyrrolidone (PVP),
polyethylene glycol (PEG). This is a large improvement in the synthesis of silver nanoparticles
because the capping agent having large molecule weight limits the electrical properties of silver
nanoparticles. Besides, we can easily reduce the gluconic acid coat during the procedure of
extracting silver nanoparticles for application related to electrical properties of silver
nanoparticles. From the TEM results we found that colloidal silver nanoparticles prepared
by using glucose is well dispersed in the solution over 60 days and have particles size about
70 nm.
Keywords: silver nanoparticle, chemical reduction, particle size control

INTRODUCTION using these capping agents will reduce

In the past decades, the synthesis of
metallic nanoparticles ranging in size from 1
nm to 100 nm, has been intensively studied
because of their fundamental scientific
interest and their many useful applications
such optical sensors, biological labels or
conducting deposits. Nanoparticles have
been studied for a long time including
gold, silver, platinum, or copper. They
exhibit outstanding electrical, optical,
magnetic, etc. properties that their bulk
counterparts will not be able to reveal.
There are many methods for metallic
nanoparticles synthesis including
chemical reduction [2, 3], thermal
decomposition [4, 5], polyol [1, 6], laser
ablation, electron beam irradiation and in
situ chemical synthetic route.
Nowadays according to the new trend of
electronic industry, metallic nanoparticles
are used to make conductive inks [3] that
can be used to print electrical paths on
different types of substrates. There have
been many successful studies on inks based
on silver (Ag) as metallic nanoparticles.
Silver nanoparticles have many special
characteristics that are of great advantage to
make and preserve ink. Most of silver
nanoparticles, used to make conductive inks,
are synthesized by chemical reduction
method using large molecule weight capping
agents such as PVP, PEG, etc… Method
electrical properties of silver conductive
inks. In this method, we use glucose which
has smaller molecule weight than PVP, PEG
as capping agent to synthesize silver
nanoparticles. And this method has more
effective in increasing the electrical
properties of silver nanoparticle ink than
method using PVP or PEG as capping
agents. However, using glucose as capping
agent has difficulty in controlling the
stability of silver nanoparticles in the
solution. Silver nanoparticles are very easily
agglomerated, oxidized and has low
stability. After many studies, we have
successfully synthesized silver nanoparticles
by chemical reduction method using glucose
as capping agent. The silver nanoparticles
that we synthesized are well dispersed in the
solution more than 60 days and have the
average particle size about 70nm. And we
found that the molar ratio of
C6H12O6/AgNO3 is an important factor to
control silver nanoparticle.
EXPERIMENTAL
All chemicals were analytical grade as
purchased and used without further
purification. Silver nitrate, AgNO3, was
purchased from Merck. Glucose (C6H12O6)
was purchased from Merck was used as the
capping agent. Triethanolamine (C6H15NO3,
Merck) was used as the main reducing agent
and a catalyst in order to oxidize glucose to
Proceedings of IWNA 2013, 14-16 November 2013, Vung Tau, Vietnam

form gluconic acid. Sodium hydroxide dispersed. Drops of the suspensions were
NaOH (> 98%, China) was also used to placed on a copper grid coated with carbon.
adjust the pH and accelerate the reduction
reaction in water. RESULTS AND DISSCUSTION
Glucose is first dissolved in deionized 1. Role of Triethanolamine
water. Then silver nitrate, AgNO3 (5mM) is Triethanolamine (TEA) is an amine with
dissolved in water and added to the aqueous three alcohol groups. TEA is strong bazer
solution containing the glucose while and used as the main reducing agent and a
vigorously stirring. Triethanolamine catalyst in oxidization of glucose to form
(C6H15NO3) (115mM) is dissolved in water gluconic acid [4]. The reaction can be
in a beaker and added to the synthesis written as:
solution. Color change occurres in the
aqueous phase from white to yellow. This
solution was stirred about 10 to 45 minutes.
Finally, a solution of NaOH is added to the
Therefore in this menthod, TEA is so
solution under continuous rapid stirring to
important to development of silver
allow the reaction to complete.
nanoparticles. Our study the ratio of [Ag+] to
Synthesized samples were studied by UV-
[TEA] was changed from 5 to 20 while other
vis absorption spectroscopy from a double-
parameters were kept constant.
beam spectrophotometer (Varian Cary 100)
Table 1. Effects of [TEA] to [Ag+] ratio.
in the wavelength range from 200 to 900
nm. Transmission electron microscopy Sample
W =[Ag+]/[TEA] λmax (nm)
(TEM) was used to study the particle size. s
Samples for TEM measurements were a 5 402
suspended in ethanol and ultrasonically b 10 400
c 20 405

[Ag+]/[TEA]=20 [Ag+]/[TEA]=5 [Ag+]/[TEA]=10

0.23

0.18
Absorbance (a.u)

0.13

0.08

0.03

-0.02
310 360 410 460 510 560 610
Walength (nm)

Figure 1 – UV-vis spectra of [Ag+]/[TEA]=5, [Ag+]/[TEA]=10, [Ag+]/[TEA]=20 samples

As shown in Fig. 1. and Table. 1. believe that, in sample c the amount of

indicating that the samples have peak reductant not enough to reduce Ag + ions in
absorption at a wavelength of about 400 nm. solution. In sample a, the free electrons,
Samples a and c correspond to w = 5 and w which contributed to oxidation of silver
= 20, with absorption intensity weaker and nanoparticles and decrease of particle
broader spectrum peaks than sample b. We density, were obtained after reaction due to
Proceedings of IWNA 2013, 14-16 November 2013, Vung Tau, Vietnam

large amount of reductant. Thus the rate of gluconic acid, as the main role of capping
TEA affects the density and stability of the agent of silver nanoparticles [11].
synthesized silver nanoparticles. As the result shown in 1.(Role of
2. Role of Glucose Triethanolamine), we synthesized samples
There are many factors that affect the with the ratio [Ag +] / [TEA] = 10, glucose
surface potential of nanoparticles as the concentrations ranged from 20 to 30 mM
particle diameter, the character of metals, and other parameters were kept constant.
solvents and especially by the capping agent Data synthesis and absorption peaks in
cover on the particle surface. In this method, Table. 2.
we use glucose, which is oxidized to

Table 2. Effects of glucose concentrations.

Samples CM of Glucose (mM) [Ag+]/[TEA] [C6H12O6] / [Ag+] λmax (nm)
d 20 10 11 400
e 25 10 11 450
f 30 10 11 450

60 days 1 day
0.35

0.3

0.25
Absorbance (a.u)

0.2

0.15
A B
0.1

0.05

0
310 360 410 460 510 560 610
Wavelength (nm)

Figure 3 – UV-vis spectra of d sample after 1 day and 60 days. (A)

UV-vis spectra of e and f samples. (B)

According to Table. 2. and Fig. 3.(B) affects the particle size distribution and
absorption wavelengths shift from 400 nm stability of silver nanoparticles in solution.
to 450 nm the increase of glucose As mentioned above, the glucose oxidation
concentration from 20 mM to 25 mM and 30 reaction with the free electrons produced by
mM. We found the appearance of the reaction below. The free electrons affect
agglomeration at the bottom of bottle e and f the stability of the silver nanoparticles in
after prepared for 3 days. We believe that solution.
the increased concentration of glucose R-CHO + 2-OH
-
R-COOH + H2O + 2e
 Proceedings of IWNA 2013, 14-16 November 2013, Vung Tau, Vietnam

25

20

15

Sample e (%)
10
ncy
que
Fre

0
60 64 68 72 76 80 84 88 92 96
Size (nm)

12

10

Sample d 6

Frequency (%)
4

0
55 60 65 70 75 80
Size (nm)

Figure 4 – Transmission electron micrographs of e and d samples

TEM results in Fig. 4. shown that the
particle size of sample d mainly between 65
and 70 nm, and 76 to 84 nm of sample e.
The particle size distribution of sample e is over 60 days and have particles size about
larger than sample d and appropriate to our
analysis of the UV-vis spectrum above. As
observing and in Fig. 3.(A) we also found
that sample with concentrations of glucose
at 20 mM has good stability after 60 days.
Thus, direct observation, UV-vis and TEM
results show that great influence of glucose
on the stability and the particle size
distribution of silver nanoparticles.
CONCLUSION
In this paper, silver nanoparticles were
successfully synthesized by chemical
reduction method. Using glucose as capping
agents which have smaller molecular weight
than common capping agents have large
molecular weight. This is a large
improvement in the synthesis of silver
nanoparticles because the capping agent
having large molecule weight limits the
electrical properties of silver nanoparticles.
From the TEM results we found that
colloidal silver nanoparticles prepared by
using gulose is well dispersed in the solution
70 nm. Despite this can not be considered
enough for a real world application in
conductive ink synthesis, it lays the ground
for future development towards a better
control on silver nanoparticles synthesized
by chemical reduction.
Acknowledgment
The authors appreciate the financial support
of Vietnam National University in Ho Chi
Minh City.
References
[1] Woo K, Kim D, Kim J S, Lim S and
Moon J Ink-jet printing of Cu#Ag-based
highly conductive tracks on a transparent
substrate Langmuir 25 (2009) 429-433
[2] Niasari M S, Davar F Synthesis of
copper and copper(I) oxide nanoparticles
Proceedings of IWNA 2013, 14-16 November 2013, Vung Tau, Vietnam
by thermal decomposition of a new
precursor Material Letters 63 (2009) 441-
443
[3] Park B K, Kim D, Jeong S, Moon J,
Kim J S Direct writing of copper conductive
patterns by ink-jet printing Thin Solid Films
515 (2007) 7706–7711
[4] Revathi Janardhanan, Murugan
Karuppaiah, Tata Narsinga Rao Synthesis
and surface chemistry of nano silver
particles Polyhedron 28 (2009) 2522–2530
[5] Mallick K, Witcomb M J and Scurrell M
S In situ synthesis of copper nanoparticles
and poly(o-toluidine): A metal–polymer
composite material European Polymer
Journal 42 (2006) 670–675
[6] Lee Y, Choi J R, Lee K R, Stott N E and
Kim D Large-scale synthesis of copper
nanoparticles by chemically controlled
reduction for applications of inkjet-printed
electronics Nanotechnology 19 (2008) 415-
604
[7] Chien Mau Dang, Chinh Dung Trinh,
Dung My Thi Dang, Eric Fribourg–Blanc
Characteristics of colloidal copper particles
prepared by using polyvinyl pyrrolidone
and polyethylene glycol in chemical
reduction method International Journal of
Nanotechnology 10 (2013) 296-303
[8]S.Ayyappan, G.N. ubbanna,
R.Srinivasa Gopalan, C.N.R. Rao
Nanoparticles of nickel and silver produced
by the polyol reduction of the metal salts
intercalated in montmorillonite Solid State
Ionics 84 (1996) 271-281
[9] Jacqueline Belloni Metal nanocolloids
Current Opinion in Colloid & Interface
Science 1 (1996) 184-196
[10] M. J. Pawar, S. S. Chaure Synthesis of
CdS nanoparticles using glucose as a
capping agent Chalcogenide Letters 6
(2009) 689 –693
[11] Hong Peng, Anshu Yang, Jianghua
Xiong Green, microwave-assisted synthesis
of silver nanoparticles using bamboo
hemicelluloses and glucose in an aqueous
medium Carbohydrate Polymers 91 (2013)
348–355