Materials Chemistry and Physics xxx (2006) xxx–xxx

Preparation of Au colloids by polyol process using

NaHCO3 as a buffering agent
Young-ho Lee, Dae-wook Kim, Seung-il Shin, Seong-geun Oh ∗
Department of Chemical Engineering, Hanyang University, Seoul 133-791, Republic of Korea
Received 29 June 2005; received in revised form 14 November 2005; accepted 5 December 2005

Abstract
Au nanoparticles were synthesized by polyol process with sodium bicarbonate (NaHCO3 ) as a pH-buffering agent. The introduction of NaHCO3
to polyol process made it possible to lower the reaction temperature and shorten the reduction time. In this study, the effects of the NaHCO3 /Au
weight ratios and the PVP concentrations on the reduction rate of AuCl4 − and the particle size of Au nanoparticles were investigated. The
NaHCO3 /Au weight ratio was varied from 0.2 to 10. The reduction rate of AuCl4 − was observed by the speeds of the color changes of the mixtures.
UV–vis spectra and electron microscopic images indicated that the size of Au nanoparticles was determined by the NaHCO3 /Au weight ratios and
the PVP concentrations.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Gold; Nanoparticles; Polyol; Sodium bicarbonate; PVP

1. Introduction chemical reduction agent free method. In this process, metal

Nanoparticles have been extensively investigated owing
to their unique physical properties, chemical reactivity, and
potential application [1–3]. The potential applications of metal
nanoparticles are mainly due to the quantum size effect [4–7]
which is derived from a dramatic reduction of the number of
free electrons in nanoparticles smaller than 5 nm, as exemplified
by specific size-dependent catalytic, optical, electronic, and
magnetic properties.
In order to obtain metal nanoparticles with desirable
properties, diverse approaches to the preparation of metal
nanoparticles have been reported [8–12]. Among other meth-
ods, chemical reduction techniques, such as electrochemical
synthesis, microwave polyol process, polyol process, pho-
tochemical reduction and ␥-irradiation method, have been
extensively investigated because these methods can be imple-
mented under simple and mild conditions and can be used to
prepare nanoparticles on a large scale.
There has been a recent innovation to prepare metal nanopar-
ticles using liquid polyols such as ethylene glycol, which was
named the polyol process [13]. Polyol process is known as a
∗ Corresponding author. Tel.: +82 222200485; fax: +82 222944568.
E-mail address: seongoh@hanyang.ac.kr (S.-g. Oh).
ions are mainly reduced by redox reaction between the metallic
precursor and the solvent; the reduction of metal ions is greatly
governed by
E, the difference between the oxidation poten-
tial of solvent and the reduction potential of metal species at
a given temperature. Generally, polyols such as ethylene gly-
col are used as a reducing agent as well as solvent for the
reduction reaction. In typical procedure, the metal precursors
are suspended or dissolved in solvent. The resultant metal pre-
cursor suspensions or solutions are heated with reflux, and then
the metallic particles are formed. In the presence of a suitable
polymer stabilizer, for example, PVP, this method gives metal
nanoparticles and their stable colloids. This method is a use-
ful preparation method with great potential possibility because
of the relatively easier control of the resulting metal nanoparti-
cles and nanostructures via the control of experimental condi-
tions. Using this method, size-controlled and shape-controlled
synthesis of metal nanoparticles have been accomplished. Actu-
ally, dissolution of appropriate amount of metal precursors in
ethylene glycol at room temperature yields colloidal metal dis-
persions, but the kinetics of the process is so slow. So, to
accelerate the reduction rate of metal ions, generally, thermal
energy is applied to the system and PVP is added into the
system. As a result, the size and size distribution of metal
particles greatly governed by reaction temperature and PVP con-
centration because the nucleation and growth step are mainly

0254-0584/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
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2 Y.-h. Lee et al. / Materials Chemistry and Physics xxx (2006) xxx–xxx

Table 1
Synthesis conditions and characteristics for PVP-stabilized Au colloids
Sample code Weight ratio PVP (g) Extinction Stability Average Standard
(NaHCO3 ):(Au) peak (nm) diameter (nm) deviation (nm)

A1 10:1 2 523 S 11.65 3.67

A2 5:1 2 524 S 11.82 4.11
A3 3:1 2 531 S 15.13 7.52
A4 1:1 2 534 S 19.75 5.36
A5 1:5 2 – U 257.70 71.37
B1 10:1 1 526 S 12.78 3.54
B2 5:1 1 527 S 14.82 5.16
B3 3:1 1 539 S 23.70 5.06
B4 1:1 1 – U 315.41 39.13
B5 1:5 1 – U – –

Reaction time: 24 h; S: stable; U: unstable.

depend on the reaction rate during the particles formation period 2.3. Characterization
[14–16].
Silvert and Tekaia-Elhsissen [17] synthesized submicronic Particle size and morphology were investigated by transmission electron
microscopy (TEM, JEOL model, JEM2000-EX II) and field emission scanning
gold particles by polyol process and investigated the effects of
electron microscopy (FE-SEM, JEOL Model JSM-6340F). For TEM investiga-
reaction temperature and PVP concentration on the size and
size distribution of gold nanoparticles. Carotenuto et al. syn-
thesized gold nanoparticles with d = ∼20 nm by the reduction
of the concentration of metal precursors and the higher ratio
of PVP/HAuCl4 [18,19]. However, it is difficult to obtain the
concentrated gold colloid with nanometer-sized particles by con-
ventional polyol method.
In this study, sodium bicarbonate (NaHCO3 ) was used as
a pH-buffering agent to accelerate the formation rate of Au
nanoparticles, which can make it possible to prepare Au nanopar-
ticles with the size of below 20 nm in diameter because fast
reduction gives burst nucleation. In addition, higher concentra-
tion Au nanoparticles can be obtained at lower reaction tempera-
ture compared with conventional polyol method. The size of Au
nanoparticles was controlled by the variation of the NaHCO3 /Au
weight ratio and the PVP concentration.

2. Experimental

2.1. Materials

Tetrachloroauric acid (HAuCl4 ·3.5H2 O) was purchased from Kojima Chem-

icals. Sodium bicarbonate (NaHCO3 , Cica-reagent, Kanto Chemical Co., Inc.)
was used as a reducing agent and poly(vinyl pyrrolidone) (PVP, Aldrich, Av.
Mw 40,000) was used as a protecting agent. Ethylene glycol (EG, 99.5%) was
obtained from Junsei Chemicals. All chemicals were used without further purifi-
cation.

2.2. Preparation of Au colloids

Colloidal Au nanoparticles were prepared by polyol process. Composition

and characteristic for each reaction condition are shown in Table 1. The 100 mL
two-neck round bottom flask was charged with NaHCO3 , PVP and 18 mL of
ethylene glycol. The flask was placed in the oil bath and the mixture was heated
with reflux at 80 ◦ C for 2 h under mild stirring. When all solutes were completely
dissolved in ethylene glycol, 2 mL of HAuCl4 ·3.5H2 O solution (50.77 mM, in
ethylene glycol) was quickly added and the color of the mixture immediately
changed except for A4, A5, B4 and B5 samples. The mixture was heated with
reflux at 80 ◦ C for 4 h. The Au concentration was fixed to 0.1% (w/v) throughout
all experiments. Fig. 1. UV–vis spectra of samples: (a) 2 g of PVP; (b) 1 g of PVP.
 Y.-h. Lee et al. / Materials Chemistry and Physics xxx (2006) xxx–xxx 3

tion, Au colloids were treated as follows; a drop of Au colloid was placed on 3. Results and discussion
the TEM grid and was dried in drying oven at 40 ◦ C for 1 day before obser-
vation. In the cases of A5 and B4, for SEM investigation, Au colloids were
3.1. Mechanism
centrifuged at 3000 rpm. Supernatant was removed and the precipitates were
washed with ethanol. This centrifugation, decantation and redispersion cycle
was repeated three times and then, Au particles were dried in a vacuum oven at In polyol process, the formation of metal particles by ethylene
40 ◦ C over 6 h. UV–vis absorption spectra were taken at room temperature on a glycol probably involves the following redox reactions:
Hewlett Packard 8453 spectrometer using a quartz cuvette with an optical path
of 1 cm. For UV–vis absorption spectra, all samples were diluted with ethylene
glycol. 2HOCH2 –CH2 OH → 2CH3 CHO + 2H2 O (1)

Fig. 2. Electron microscopic images and size distributions of samples (2 g of PVP): (a) A1; (b) A2; (c) A3; (d) A4; (e) A5 (scale bar: 50 nm (A1–A4), 1 ␮m
(A5)).
4 Y.-h. Lee et al. / Materials Chemistry and Physics xxx (2006) xxx–xxx

Fig. 2. (Continued ).

n 3.2. Effects of sodium bicarbonate on the formation of Au

nCH3 CHO + Mn+ → CH3 CO–COCH3 + M0 + nH+
2 nanoparticles
Actually, the dissolution of appropriate amount of metal salt
in ethylene glycol at room temperature yields colloidal metal dis-
persion, but the kinetics of the process is so slow [14]. Since the
polyol process is based on a redox reaction between the metallic
precursor and the solvent, the reduction of metal ions is greatly
governed by the difference between the oxidation potential of
ethylene glycol and the reduction potential of metal species at
a given temperature. In polyol process, the reaction rate can be
accelerated by the thermal energy provided by heating, the use
of PVP, and an increase in pH of the solution.
NaHCO3 is decomposed into sodium carbonate, carbon diox-
ide and water above about 50 ◦ C. The decomposition of sodium
bicarbonate is represented by the following reaction:
2NaHCO3 → Na2 CO3 + CO2 + H2 O
The generation of water makes the carbonate ions be dis-
solved more easily, while sodium bicarbonate is not completely
dissolved in ethylene glycol. The carbonate ions act as a pH-
buffering agent and increase the pH of solvent. As a result, the
protons are consumed by carbonate ions, which make the reduc-
tion rate be accelerated according to Le Chatelier’s principle (see
Eq. (2)).
(2)
The addition of NaHCO3 increases pH of the solution and
thus leads to an increase in the reduction rate of gold precursor. In
this section, to investigate the effect of NaHCO3 on the formation
of Au nanoparticles, the NaHCO3 /Au weight ratio was varied
from 0.2 to 10.
It is difficult to observe time-evolution behavior of UV–vis
spectra due to the fast reduction rate. So, the reduction rate
was checked by the time to complete the color change of the
mixture. The reduction rate was greatly dependent on the ratio
of NaHCO3 to Au. When the amount of PVP added into the
reaction medium was fixed to 2 g, the colors of the first three
samples (A1–A3) changed in a few seconds. In the case of
A4, when HAuCl4 solution was added, the color of the mixture
(3) grew darker and completely changed to dark purple after 10 min.
When NaHCO3 /Au weight ratio was 0.2, the color of the mixture
changed slowly and much longer time was required to complete
the reduction of AuCl4 − . For 1 g of PVP, the time to complete the
color change also increased with a decrease in the concentration
of NaHCO3 . This fact implies that the NaHCO3 /Au weight ratio
determines the reduction rate of AuCl4 − , that is, the reduction
rate of AuCl4 − increases with an increase of the NaHCO3 /Au
weight ratio.
 Y.-h. Lee et al. / Materials Chemistry and Physics xxx (2006) xxx–xxx 5

The effect of NaHCO3 on the size and size distribution was
investigated by UV–vis spectrophotometer and TEM. Fig. 1
shows the UV–vis absorption spectra of Au colloids and Table 1
lists the extinction peak wavelength (λmax ) of each sample. A1
has the extinction peak wavelength at 523 nm and the λmax
moves to longer wavelength with the decrease of the NaHCO3
concentration. For the lower concentration of PVP, this ten-
dency was also observed. According to Mie’s theory for the
optical properties of metal colloids, the surface plasmon reso-
nance (SPR) band shifts to longer wavelength when the particles
size increases [20–22]. Thus, it can be seen that the size of Au
nanoparticles increase with the decrease of the NaHCO3 /Au
weight ratio from UV–vis absorption spectra of Au colloids.
This explanation was further confirmed by TEM observation;
that is, the average particle size increases with the decrease of
the NaHCO3 /Au weight ratio as shown in Fig. 2 and Table 1. In
Fig. 4, when NaHCO3 /Au weight ratio was above 5, the mean
particle size slightly decreased with the NaHCO3 concentration.

Fig. 3. Electron microscopic images and size distributions of samples (1 g of PVP): (a) B1; (b) B2; (c) B3; (d) B4; (e) B5 (scale bar: 50 nm (B1–B3), 1 ␮m (B4–B5)).
6 Y.-h. Lee et al. / Materials Chemistry and Physics xxx (2006) xxx–xxx
Fig. 3. (Continued ).
However, in the case of low NaHCO3 /Au weight ratio, the
particle size largely decreased with the NaHCO3 concentration.
When 1 g of PVP was utilized, a similar tendency was also
observed as shown in Fig. 3 and Table 1. It is explicit that
the size of Au nanoparticles is dependent on the NaHCO3 /Au
weight ratio, that is, the higher NaHCO3 /Au weight ratio is,
the smaller the size of Au nanoparticles. However, for high
NaHCO3 concentration, the change of the NaHCO3 /Au weight
ratio hardly affects the size of Au particles.
From these results, it can be seen that higher NaHCO3 /Au
weight ratio induces the fast reduction rate of AuCl4 − , which
make the particle size decrease because fast reduction rate gives
a large number of nuclei via burst nucleation. As it is well known,
the size of metal nanoparticles depends on the reduction rate of
the metal precursor [23–25]. In previous papers, the presence of
NaOH greatly accelerated the reduction rate of the metal precur-
sor and reduced the particle size compared with the absence of
NaOH [26–28]. Thus, pH of solution plays an important role for
the determination of the particle size. During the experiments,
Na2 CO3 formed by the decomposition of NaHCO3 acts as a
pH-buffering agent and the protons are consumed by carbonate
ions. In Eq. (2), the consumption of protons makes the reduc-
tion rate be accelerated according to Le Chatelier’s principle.
Thus, an increase in the concentration of NaHCO3 accelerates
the reduction rate of AuCl4 − and this leads to the formation of
smaller Au particles via rapid nucleation.
3.3. Effects of PVP on the formation of Au nanoparticles
Silvert and Tekaia-Elhsissen suggested that PVP acts not only
as a protective agent but also as a reducing agent [17]. To inves-
tigate the effect of PVP on the formation of Au nanoparticles, 1
and 2 g of PVP were utilized for each weight ratio of NaHCO3
to Au. When NaHCO3 /Au weight ratio was above 3, the color
change occurred within a few seconds (A1–A3 and B1–B3) and
it was difficult to determine the reduction rate. However, when
the NaHCO3 /Au weight ratio was 1, B4 required much longer
time to complete the color change than A4. This observation
shows that an increase in the concentration of PVP leads to the
suppression of the growth of metal particles and an increase in
the reduction rate.
As can be seen from Table 1 and Fig. 1, when 1 g of PVP
was utilized, the SPR band was shifted to longer wavelength.
This means that the size of Au nanoparticles increases with a
decrease in the PVP concentration [20–22]. However, the degree
of the shift of the SPR band is not constant and increases with
a decrease in the NaHCO3 /Au weight ratio. The variation of
λmax between A1 and B1 is 3 nm and smaller than that of λmax
 Y.-h. Lee et al. / Materials Chemistry and Physics xxx (2006) xxx–xxx 7

the concentration of NaHCO3 decreases, the PVP concentra-

tion determines the reduction rate of AuCl4 − and the size of Au
nanoparticles.

Acknowledgement

This research was funded by Center for Ultramicrochemical

Process Systems sponsored by KOSEF.

References

[1] G. Craighead, Science 290 (2000) 1532.

[2] S.R. Quake, A. Scherer, Science 290 (2000) 1536.
[3] E.W.H. Jager, E. Smela, O. Inganas, Science 290 (2000) 1540.
[4] N. Toshima, T. Yonezawa, N. J. Chem. 22 (1998) 1179.
[5] T. Yonezawa, H. Matsune, T. Kunitake, Chem. Mater. 11 (1999) 33.
[6] C. Petit, A. Taleb, M.P. Pileni, Adv. Mater. 10 (1998) 259.
Fig. 4. Plots of the mean size (nm) of the Au nanoparticles as a function of the [7] T. Yonezawa, S. Onoue, N. Kimizuka, Langmuir 16 (2000) 5218.
NaHCO3 /Au weight ratio (solid line: 2 g of PVP; dotted line: 1 g of PVP). [8] K. Torigoe, K. Esumi, Langmuir 9 (1993) 1664.
[9] K. Esumi, T. Tano, K. Torigoe, K. Meguro, Chem. Mater. 2 (1990) 564.
[10] A. Henglein, in: H.F. Bicke (Ed.), Modern Trends in Colloid Science
between A3 and B3 (8 nm). This means that the difference of
and Chemistry and Biology, Birkhauser verlag, Stuttgart, 1985, p. 126.
the particle size between A3 and B3 is larger than that between [11] M.T. Reetz, W. Helbig, J. Am. Chem. Soc. 116 (1994) 7401.
A1 and B1. Fig. 4 shows that
davg increases with decreasing [12] J. Turkevich, G. Kim, Science 169 (1970) 873.
in the NaHCO3 /Au weight ratio (
davg = davg (B) − davg (A) for [13] F. Fiévet, in: T. Sugimoto (Ed.), Surfactant Science Series 92 (Fine
the fixed weight ratio of NaHCO3 to Au). Particles), Marcel Dekker, New York, 2000, p. 460.
[14] P.-Y. Silvert, R. Herrera-Urbina, N. Duvauchelle, V. Vijayakrishnan, K.
It was already mentioned that the presence of PVP in reduc-
Tekaia-Elhsissen, J. Mater. Chem. 6 (1996) 573.
tion medium not only prohibits the aggregation of the Au par- [15] Y. Sun, Y. Yin, B.T. Mayers, T. Herricks, Y. Xia, Chem. Mater. 14
ticles but also promotes the cluster growth [17]. For relatively (2002) 4736.
low NaHCO3 concentration, the concentration of carbonate ions [16] S.H. Im, Y.T. Lee, B. Wiley, Y. Xia, Angew. Chem. Int. Ed. 44 (2005)
is not high to consume the protons and then NaHCO3 is not an 2154.
[17] P.-Y. Silvert, K. Tekaia-Elhsissen, Solid State Ionics 82 (1995) 53.
important factor to determine the reduction rate. In this case,
[18] G. Carotenuto, L. Nicolas, J. Mater. Chem. 13 (2003) 1038.
PVP plays an important role for the determination of the reduc- [19] F. Bonet, V. Delmas, S. Grugeon, R. Herrera Urbina, P.-Y. Silvert, K.
tion rate and an increase in the PVP concentration accelerates Tekaia-Elhsissen, Nanostruct. Mater. 11 (1999) 1277.
the reduction rate of AuCl4 − and this leads to form a smaller [20] H.C. van de Hulst, Light Scattering by Small Particles, Dover, New
Au particles. York, 1957.
[21] K. Nakamura, T. Kawabata, Y. Mori, Powder Technol. 131 (2003) 120.
[22] Y. Sun, Y. Xia, Analyst 128 (2003) 686.
4. Conclusions [23] J.A. Creighton, D.G. Eadon, J. Chem. Soc., Faraday Trans. 87 (1991)
3881.
In summary, Au nanoparticles were synthesized in the pres- [24] D.G. Duff, P.P. Edwards, F.G. Johnson, J. Phys. Chem. 99 (1995) 15934.
ence of NaHCO3 and PVP. It was confirmed that both the [25] H. Hirai, Y. Nakao, N. Toshima, J. Macromol. Sci. Chem. A 12 (1978)
1117.
NaHCO3 /Au weight ratio and the concentration of PVP affect
[26] W. Tu, H. Liu, J. Mater. Chem. 10 (2000) 2207.
the reduction rate of AuCl4 − , which determine the particle [27] W. Yu, W. Tu, H. Liu, Langmuir 15 (1999) 6.
size. At higher concentration of NaHCO3 , NaHCO3 domi- [28] S. Komarneni, D. Li, B. Newalkar, H. Katsuki, A.S. Bhalla, Langmuir
nantly determines the reduction rate of AuCl4 − . However, as 18 (2002) 5959.