Bull. Korean Chem. Soc. 2013, Vol. 34, No.

2 363
http://dx.doi.org/10.5012/bkcs.2013.34.2.363

Communications to the Editor

Nanogold Particles Produced by NaBH4 Reduction of Gold Salt in the

Presence of Laponite Sol
Seung-Kyu Yang and Youhyuk Kim*
Department of Chemistry and Institute of Basic Sciences, College of Advanced Sciences, Dankook University,
Cheonan, Chungnam 330-714, Korea. *E-mail: hyukim@dankook.ac.kr
Received November 2, 2012, Accepted November 30, 2012
Key Words : Nanogold particles, Laponite, X-Ray diffraction, UV-vis, TEM

In the last few decades, there has been considerable effort

in preparing and characterizing nanostructured materials.1
Layered inorganic solids such as polysilicates, double hydroxide, perovskites and clay minerals are important constituents of these assemblies because of their ability to provide
interlamellar space, and their large active surface area.2
Laponite is a synthetic polycrystalline clay similar in structure and composition to natural hectorite of the smectite
group. The sodium ions in the central layer of laponite are
exchangeable, and in aqueous dispersions, these ions diffuse
into the water, and plate-like particles with negatively charged faces are formed.3,4 Among nanoparticles, colloidal metal
or metal oxide particles have been intensively studied because
of their unique optical and catalytic properties and their
biomedical applications.5 There have been many reports on
the synthesis of nanoparticle/clay composites.6-10 Metal hydroxides of iron, chromium, cobalt, manganese and cerium in
acetic acid solutions were used to exchange the sodium ions
in laponite, and their corresponding nanometal oxidelaponite composite products were obtained by calcination of
adsorptions of these precursor solutions at 500 oC in air.11
The preparation and characterization of nanogold/laponite
composite were examined in this study. For this purpose,
gold(III) chloride solution in dilute HCl was reduced with
sodium borohydride in the presence of laponite.12 UV-vis
spectra of different concentrations of nanogold sols are shown
in Figure 1. In Figures 1(a) and (b), very broad absorption
peaks are observed, and apparent surface plasmon resonance
absorptions of nanogold particles are not observed due to the
very low concentration of nanogold particles. Alternatively,
characteristic surface plasmon resonance absorption of
nanogold particles can be observed at about 520 nm in high
concentrations of nanogold (Figures 1(c), (d) and (e)). With
the increase of gold content, the absorption peak position is
shifted toward higher wavelength, from 518 nm to 521 nm.
This red shift can be related to the growth of nanogold
particles with the increase of gold content. It is known that
the surface plasmon resonance absorption of gold nanoparticles is very sensitive to particle aggregation and variations in surroundings, and strongly influenced by chemical
modifications of the particle surfaces.14-16 The growth of
nanogold particles has also been observed in TEM micrographs, as shown in Figure 2. The particle size is changed

Figure 1. UV-vis absorption spectra of gold colloids in the

presence of laponite as a function of HAuCl4 concentrations: (a)
0.05, (b) 0.25, (c) 0.50, (d) 2.5, (e) 5.0 mmol.

from about 3 nm to about 15-20 nm. With a low concentration of nanogold particles, not many particles were observed,
and these results agree well with those of UV-vis spectra,

Figure 2. TEM micrographs of nanogold particles in the presence

of laponite prepared in various concentrations of HAuCl4: (a) 0.25,
(b) 0.50, (c) 2.5, (d) 5.0 mmol.

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Bull. Korean Chem. Soc. 2013, Vol. 34, No. 2

Communications to the Editor

nm, respectively. This result is consistent with that of TEM

in Figure 2. In conclusion, laponite RD can be used as a
protective colloid to give stable nanogold. Although there
are many reports about surfactant molecules intercalated in
laponite18, the interaction between nanogold and laponite is
not reported. This study shows that nanogold particles of
cryogel are adsorbed to the external surfaces rather than
intercalating into interlayer of laponite.
Acknowledgments. The present research was conducted
under the research fund of Dankook University in 2010.
References
Figure 3. XRD patterns of cryogels with different concentrations
of HAuCl4: (a) the parent Laponite RD, (b) 0.05, (c) 0.25, (d)
0.50, (e) 2.5, (f) 5.0 mmol.

which show very broad peaks.

Figure 3 shows XRD patterns of the clay composite
loaded with nanogold particles at different gold content. The
XRD patterns of the parent Laponite RD shows broad peaks
with a basal d001 spacing of 1.37 nm, corresponding to an
interlayer distance of 0.41 nm due to the hydrated sodium
ions occupying the interlayer space. The interlayer distance
is obtained after subtracting the thickness of the intrinsic
silicate layer (~0.96 nm) from the basal spacing.17 A very
small increase of the interlayer distance is observed after
nanogold generation, as shown in Figures 3(b) and (c). The
basal d001 spacing value of Laponite RD after nonogold
incorporation in Figures 3(b) and (c) is about 1.42 nm, and
corresponds to an interlayer distance of 0.46 nm. This value
shows that the hydrated sodium ions are still occupying the
interlayer space. The intercalation of nanogold into the
interlayer of laponite is excluded, because the particle sizes
obtained from the TEM micrographs in Figure 2(a) are too
large to be accommodated between the layers of the clay.
The sharpness of the d001 reflection in Figures 3(b) and (c)
suggests that the layers of laponite after freeze-drying are
stacked face to face in ordered tactoids. With high nanogold
concentration, the nanogold particles in laponite showed Xray patterns characteristic of gold, although the degree of
crystallinity differed, as shown in Figures 3(d), (e) and (f).
The broadness of the d001 reflections of the laponite in
Figures 3(d), (e) and (f) confirm that laponite containing
large-size nanogold forms disordered structure with little
face-to-face stacking. Therefore, much of these nanogold
particles must be deposited on the external surfaces rather
than undergoing intercalation. The size of the nanogold
particles from the (311) reflection in the XRD patterns in
Figures 3(e) and (f) was calculated using the Scherrer
formula in order to obtain a rough estimate of the crystallite
size of the nanogold. These values are given as 14.8 and 17.7

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Laponite RD (1.00 g, 0.50 mmol of negative charge) in 1000 mL
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laponite solution and stirred for 5-10 more minutes. Separately,
analytically pure HAuCl4 (5.57 mg, 0.05 mmol) in 100 mL water
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