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Materials Today: Proceedings 5 (2018) 14057–14062 www.materialstoday.com/proceedings

SACT 2016

The effect of additive chemicals on synthesis of bismuth

nanoparticles
K. Petsoma,b, A. Kopwitthayac,*, M. Horphathumc, J. Kaewkhaoa,b, N. Sangwaranateec
a
Center of Excellence in Glass Technology and Materials Science (CEGM), Nakhon Pathom Rajabhat University, Nakhon Pathom 73000,
Thailand
b
Physics Program, Faculty of Science and Technology, Nakhon Pathom Rajabhat University, Nakhon Pathom 73000, Thailand
c
National Electronics and Computer Technology Center, Pathum Thani 12120, Thailand
c
Applied Physics, Faculty of Science and Technology, Suan Sunandha Rajabhat University, Bangkok 10300, Thailand

Abstract

Bismuth nanostructures are of interest due to unique properties such as strong diamagnetism, high magnetoresistance under
magnetic field, as well as biocompatibility compared with lead. Previous study have reported a relationship of obtained
nanostructures and synthesized conditions including pH, temperature and time during nucleation. Most of them confront
difficulties on size controlling, particularly in large volume synthesis. Therefore, the goal of this work is to simplify the synthesis
method by studying an effect of additive chemicals which are introduced to a growth solution before nanocrystal formation.
Ascorbic acid, dioctyl sulfosuccinate sodium salt (AOT) and ethanol were chosen to slow down the reaction or disturb the
micellar template. The study has shown that size of nanoparticles can be easily tuned by adding different amount of
aforementioned chemicals. According to different role in nanocrystal forming mechanism, more ascorbic acid tends to increase
diameter of obtained particles. Oppositely, more AOT has shrunk synthesized particles due to packed micelles. Loose micelles
are found in ethanol experiment leading to bigger particles in size. In addition, crystalline structure exhibited the diffraction plane
at (012), (104), and (110) with X-Ray diffraction (XRD) analysis. Field emission scanning electron microscopy (FE-SEM) was
used to determine morphology of nanoparticles, and also size distribution was confirmed by nanoparticle tracking analysis
(NTA). We also found the quench of nanocrystal formation in the presence of high concentration of ethyl alcohol.
© 2018 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Selection and/or Peer-review under responsibility of SACT 2016.
Keywords: Ascorbic acid; Docusate sodium salt; ethanol; room temperature synthesis

* Corresponding author. Tel.: +662-564-6900

E-mail address: atcha.kopwitthaya@nectec.or.th

2214-7853 © 2018 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Selection and/or Peer-review under responsibility of SACT 2016.
14058 K. Petsom et al./ Materials Today: Proceedings 5 (2018) 14057–14062

1. Introduction

Metal nanomaterials have attracted a great deal of interest because its optical [1-3], catalytic [2], magnetic [2-4],
and electrical [4] properties depends mainly on size and shape. Bismuth is one of the most interesting materials
which can transit from semi-metal to semiconductor when its crystallite is small enough [5]. Due to its highly
anisotropic Fermi surface, low carrier concentration, small effective mass, and long mean free path of the charge
carriers, bismuth nanoparticles presents outstanding catalytic and photocatalytic properties. With aforementioned
advantages, bismuth nanoparticles is widely used in various potential applications including antimicrobial agent in
biomedical sciences [6], X-Ray radiation therapy [7], thermoelectric sensor [8] and heavy-metal ion detector [9].
To date, chemical approaches are widely used to obtain bismuth nanoparticles. Typically, several methods such
as solvent-less methods [10], high temperature hydrothermal [11], pH-Dependent [12], and inversed micelles
methods [13] can be used to prepare bismuth nanostructures. However, most of them require high-temperature and
long aging time in the process.
In this work, we simplify the protocol by studying the additive chemicals to control nanostructures forming in the
nucleation process. Our protocol can be done at room temperature with the use of sodium borohydride (NaBH4) as
reducing agent. Different chemical such as ascorbic acid, dioctyl sulfosuccinate sodium salt (AOT), and ethanol
were introduced to the reaction to disturb nanocrystal formation. Different sizes of obtaining bismuth nanoparticles,
then were successfully prepared depending on concentration of the additives. Besides, our study also found the
effect of additives on volume of the prepared nanopowder. This finding will be critical information of nanopowder
mass production especially in industrial-scale preparation.

2. Material and methods

2.1 Materials

Bismuth nitrate pentahydrate (Bi(NO3)3•5H2O) purchased from CARLO ERBA Reagents. Nitric acid (HNO3,
70%) purchased from J.T.Baker. Sodium hydroxide (NaOH) purchased from Ajax Finechem. Sodium oleate (SOA)
purchased from TOKYO CHEMICAL INDUSTRY. Tartaric acid (TA, H2C4H4O6) purchased from Ajax Finechem.
Ascorbic acid (C6H8O6) purchased from Sigma-Aldrich. Dioctyl sulfosuccinate sodium salt (AOT) purchased from
Sigma-Aldrich. Ethanol (C2H6O 99.99%) purchased from MERCK. And sodium borohydride (NaBH4) purchased
from Fluka Analytical. All the reagents were used without further purification.

2.2 Synthesis of Bismuth nanoparticle

Bismuth nanoparticles were synthesized under an aqueous condition. In a typical preparation, the mixture
containing 40 ml (0.01 M) of Bi(NO3)3•5H2O, 40 ml (0.04 M) of H2C4H4O6 and 6 ml of HNO3 were stirred with
maximum speed. Then, 0.4 g of NaOH in 20 ml distilled water was added to the suspension and stirred at room
temperature to get a transparent solution. Use 20 ml of the mixture above, then, 10 ml (2 mM) of SOA was added
into the solution. In the additive study experiments, additive chemicals were introduced to the mixture at various
concentrations. For example, 100-500 μl of ascorbid acid (0.1mM), 100-500 μl of AOT (0.1mM), and ethanol in
distilled water at ratio of 0:10, 2:8, 5:5, 8:2. In the final step, 800 μl (7 mM) of fresh NaBH4 solution was quickly
added. Upon the addition of reducing agent, the solution was observed to change from cloudy-colorless suspension
to black solution. The resulting black precipitates were filtered, and then washed with distilled water and absolute
ethanol for several times to remove excess chemicals. Bismuth nanopowder was dried at 80 °C for 15 min.

2.3 Characterizations

The crystallization of bismuth nanoparticles were determined by X-ray diffraction (XRD) using a Rigaku, Japan/
TTRAX III diffractometer with Cu K1 (λ= 1.5406A˚) radiation in a 2θ range of 10–80 at room temperature. The
morphology and particle size of bismuth nanoparticle were characterized by field emission scanning electron
microscopy (FE-SEM), Hitachi SU-8030 with power of electron beam 5 kV. All samples were taken at the same
 K. Petsom et al./ Materials Today: Proceedings 5 (2018) 14057–14062 14059

condition of power source. Size distribution measurements were also carried out by counting at least 500 particles.
The hydrodynamic diameters of nanoparticles were measured by Nanosight-NS500 with nanoparticle tracking
analysis software, NTA 3.0. All samples were dissolved in 2% Tween 80 and sonicated for 5 minutes before
measurement.

3. Results and discussion

In the micellar system, different chemicals introduced to solution can play different role in the reaction. Scheme 1
demonstrates the mechanism of nanocrystal formation in this report. When optimum concentration of SOA is
dissolved in water, nanomicellar are formed [14]. In the presence of AOT, the micelle will be packed due to the
increasing of surfactant concentration. Oppositely, ethanol has ability to loose a micelle because alkyl chain of the
surfactant is soluble in alcohol [15]. Taking advantages of these properties, easy way to tune particles size is
proposed here. In addition, weak reducing agent like ascorbic acid tends to retard the reaction. Therefore, we
observed few minutes delay in nucleation process.

Scheme. 1 Possible mechanisms of bismuth nanoparticles formation in the presence of additives

500nm 500nm 500nm

Fig. 1. FE-SEM images of bismuth nanoparticle synthesized in the presence of (a) 300 μl of ascorbic acid, (b) 300 μl of AOT, and (c) ethanol:
water in a ratio of 8:2.

As-prepared bismuth nanoparticles were examined using Field-Emission Scanning Electron Microscope as
shown in Fig. 1. Most of particles are spherical-like shape, although some irregular shapes are occasionally seen.
The pH of growth solution were also investigated to see the pH-dependent effect which have reported recently [12].
14060 K. Petsom et al./ Materials Today: Proceedings 5 (2018) 14057–14062

In our method, we did not observe the difference in shape when pH of growth solution is in the range of 8-11. Fig. 2
shows size distribution of bismuth nanoparticles prepared by different additives.

Fig. 2. Size distribution and standard deviation of bismuth nanoparticle synthesized in the presence of (a) 300 μl of ascorbic acid, (b) 300 μl of
AOT, and (c) ethanol: water in a ratio of 8:2.

To further investigate hydrodynamic diameter of nanoparticles at various concentration of different chemical

additives, we tracked the particle motions with nanoparticle tracking analysis system (NTA 3.0). Each sample was
dissolved in water with 2% tween80 to make them water-soluble. We found that increasing concentration of
ascorbic acid in the growth solution leading to a bigger nanocrystal forming, Fig. 3a. However, ascorbic acid has not
potentially changed the diameter of bismuth nanoparticles. It obviously quenched the crystal formation by delaying
the nucleation time and reduced the product. As shown in Table 1, 15.3 mg of bismuth nanopowder can be collected
from the reaction in the presence of 100 μl of ascorbic acid. By increasing concentration almost 5 times of ascorbic
acid, only 10.1 mg can be found which mean more than 30% loss. It is worth noting that ascorbic acid is known for
weak reducing agent which widely uses in gold nanorods formation. Ascorbic acid slowly reduces gold ion to
become gold crystal, therefore, rod shape is formed [16]. Here, we found that ascorbic acid alone cannot reduce
bismuth ion to bismuth crystal. Thus, strong reducing agent NaBH4 is needed. Without ascorbic acid addition, more
irregular shapes can be observed.
An interesting effect of co-surfactant has proved by adding different amount of AOT. Hydrodynamic diameters
of bismuth nanoparticles decrease from 195.3 nm to 107.4 nm while concentration of AOT increases almost 5 times,
Fig. 3b. With a carefully surfactant removal, obtained bismuth nanopowder synthesized by adding 300 μl of AOT
weighs 138.53% comparing with adding 100 μl of AOT. For 400 and 500 μl of AOT, amount of collected
nanopowder is similar. The finding shows that adding AOT not only changes size of nanoparticles but also increases
synthesized product. On the other hand, alcohol increases size of nanoparticles from 98.5nm to 162.9 nm when the
ratio of ethanol and water increases, Fig. 3c. At higher concentration of ethanol, smaller amount of nanopowder are
observed. Although ethanol demonstrates a great potential to tune size of bismuth nanoparticles, amount of collected
nanopowder can be 21.9% by weight loss.

Fig. 3. Hydrodynamic diameter of bismuth nanoparticle synthesized in the presence of (a) 300 μl of ascorbic acid, (b) 300 μl of AOT, and (c)
ethanol: water in a ratio of 8:2.
 K. Petsom et al./ Materials Today: Proceedings 5 (2018) 14057–14062 14061

Table 1. Mass volume of prepared nanoparticles is additive material.

additive material average weight (mg)
ascorbic acid 100 μl 15.3
ascorbic acid 200 μl 14.2
ascorbic acid 300 μl 14.1
ascorbic acid 400 μl 11.1
ascorbic acid 500 μl 10.1
AOT 100 μl 10.9
AOT 200 μl 11.3
AOT 300 μl 15.1
AOT 400 μl 15.1
AOT 500 μl 15.3
DI 10 ml + Ethanol 0 ml 13.2
DI 8 ml + Ethanol 2 ml 13.1
DI 5 ml + Ethanol 5 ml 11.3
DI 2 ml + Ethanol 8 ml 11.1
DI 0 ml + Ethanol 10 ml 10.3

Fig. 4. XRD patterns of bismuth nanoparticles containing ascorbic acid 100 μl.

In addition, XRD measurements were used to determine the crystalline phase of the as-prepared bismuth
nanopowders. XRD patterns of samples containing ascorbic acid 100 μl are shown in Fig. 4. All of the reflections
can be readily indexed to the pure rhombohedral phase of Bi (JCPDS No. 004-1246).

4. Conclusion

Additive chemicals show ability in tuning size of bismuth nanoparticles and also affect the amount of prepared
nanopowder. Higher concentration of weak reducing agent like ascorbic acid yields smaller in amount of product,
similar to ethanol. Dioctyl sulfosuccinate sodium salt (AOT), oppositely, can reduce size of bismuth nanoparticles
and increase weight of synthesis powder. This study provides a room-temperature synthesis method and will be
useful for the development of industrial-scale production.

Acknowledgements

This study is supported by National Research Council of Thailand.

14062 K. Petsom et al./ Materials Today: Proceedings 5 (2018) 14057–14062

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