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Synthesis of Au/TiO2 Core–Shell Nanoparticles from Titanium Isopropoxide and Thermal

Resistance Effect of TiO2 Shell

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Japanese Journal of Applied Physics
Vol. 46, No. 4B, 2007, pp. 2567–2570
#2007 The Japan Society of Applied Physics

Synthesis of Au/TiO2 Core–Shell Nanoparticles from Titanium Isopropoxide

and Thermal Resistance Effect of TiO2 Shell
Hyun-Woo K WON, Young-Min LIM, Suraj Kumar T RIPATHY, Byoung-Gyu K IM1 ,
Min-Sang LEE2 , and Yeon-Tae Y U

Division of Advanced Materials Engineering, Research Center of Advanced Materials Development, Chonbuk National University,
Jeonju 561-756, Korea
1
Minerals and Materials Processing Division, Korea Institute of Geoscience and Mineral Resources, Daejeon 305-350, Korea
2
LM3 Group, Samsung Electro-Mechanics Co., Ltd., Suwon 443-743, Korea
(Received September 25, 2006; accepted November 29, 2006; published online April 24, 2007)

On the synthesis of Au/TiO2 core–shell structure nanoparticles, the effect of the concentration of Ti4þ on the morphology and
optical property of Au/TiO2 core–shell nanoparticles was examined. A gold colloid was prepared by mixing HAuCl4 4H2 O .
.
and C6 H5 Na3 2H2 O. Titanium stock solution was prepared by mixing solutions of titanium(IV) isopropoxide (TTIP) and
triethanolamine (TEOA). The concentration of the Ti4þ stock solution was adjusted to 0.01– 0.3 mM, and then the gold colloid
was added to the Ti4þ stock solution. Au/TiO2 core–shell structure nanoparticles could be prepared by the hydrolysis of the
Ti4þ stock solution at 80  C. The size of the as-prepared Au nanoparticles was 15 nm. The thickness of the TiO2 shell on the
surface of gold particles was about 10 nm. The absorption peak of the Au/TiO2 core–shell nanoparticles shifted towards the
red end of the spectrum by about 3 nm because of the formation of the TiO2 shell on the surface of the gold particles. The
crystal structure of the TiO2 shell showed an anatase phase. The increase in the Au crystallite size of the Au/TiO2
nanoparticles with increasing heat treatment temperature is smaller than that in the pure Au nanoparticles. This may be due to
the encapsulation of Au particles with the TiO2 shell that prevents the growth of the nanoparticle nucleation.
[DOI: 10.1143/JJAP.46.2567]
KEYWORDS: core–shell nanoparticle, gold, titanium dioxide, sol–gel method

Ag/TiO2 core–shell nanoparticles could be prepared in

1. Introduction
Core-shell structure composite nanoparticles have attract-
ed much attention for their wide range of applications such
as in microelectronics, optical limiters, optical data storage,
and as catalysts among others, which have exhibited
improved physical and chemical properties over their
single-component counterparts.1–5) Core-shell structures
have been fabricated, including semiconductor/semiconduc-
tor, semiconductor/dielectric, metal/metal, metal/semicon-
ductor, metal/dielectric, and dielectric/metal structures.6)
Among these core–shell structures, metal/semiconductor
structure nanoparticles not only maintain the quantum size
effect by overcoming coalescence due to van der Waals
forces but also enhance the stabilization of colloids under
extreme conditions through the encapsulation of nanopar-
ticles with an inert oxide shell.7–10)
A semiconducting shell around small metal nanoparticles,
such as TiO2 , can lead to the formation of composite
particles with high electronic capacitance and low leakage
rates. Due to the large difference between the intrinsic Fermi
level of the core and the conduction band energy of the
semiconductor shell, mobile electrons that diffuse within the
shell will be trapped for long periods in the core. In this
study, we deposit a TiO2 shell on the surface of gold
particles using the sol–gel method. The sol–gel method is a
useful technique because it can cohere the components of
materials to an atom or molecule level.12,13)
Mayya et al.14) have shown that core–shell Au/TiO2
nanoparticles could be obtained using an approach based on
the complexation of a titania precursor titanium(IV) bis(am-
monium lactato) dihydroxide with a polyelectrolyte fol-
lowed by hydrolysis. Zhang et al.15) have demonstrated that


E-mail address: yeontae@chonbuk.ac.kr
2567
water-in-oil emulsions using tetrabutyl titanate and these
nanoparticles have potential applications in photoinduced
electron storage and photocatalysis. Yu and Mulvaney16)
have deposited the titania shell on the surface of gold
particles using titanium oxide acethylacetonate (TOAA) in
gold sol ethanol solution with water. However, the thickness
of the titania shell could not been increased to more than
1 nm because of the faster hydrolysis of TOAA. In the above
letter, the controlled growth of the TiO2 shell on the metal
nanoparticles could not be achieved because of the rapid
hydrolysis of titanium alkoxide.
In the present paper, to form a uniform titania shell on the
Au nanoparticles and to control the thickness of the shell,
decreasing the hydrolysis reaction velocity of titanium(IV)
isopropoxide is tried using triethanolamine as the complex-
ing agent. The effects of the concentration of Ti4þ on the
morphology and optical property of Au/TiO2 core–shell
nanoparticles were examined by transmission electron mi-
croscopy and UV–vis spectrophotometry. The crystal struc-
ture and thermal resistance effect of the TiO2 shell were
investigated by X-ray diffraction analysis.
2. Experimental Procedure
2.1 Synthesis of Au colloid
A gold colloid (500 mL, 5  104 M) is prepared accord-
ing to the standard sodium citrate reduction method.17)
.
HAuCl4 4H2 O (Showa Chemicals, 99.0%) and trisodium
citrate dehydrate (Showa Chemicals, 98.0%) were used as
starting material and reductant, respectively. This method
produces a stable, deep-red dispersion of gold particles with
an average diameter of approximately 15 nm. To improve
the mutual affinity between Au nanoparticles and TiO2 ,
mercaptoundecanoic acid (MUA; Aldrich, 95%) was dis-
solved into 2.5% aqueous ammonia solution (½MUA ¼
Jpn. J. Appl. Phys., Vol. 46, No. 4B (2007)
1 mM). The MUA solution was then added to the gold
colloid and incubated for 2 h.18) Then, 1 M HCl was added
dropwise until the pH was equal to 3 to make the MUA–gold
particles flocculate. The flocculate was left to stand for one
night to sediment. The collected gold was washed with water
by centrifugation at 3800 rpm. The gold particles were
placed into 20 mL of water and re-dispersed by adding about
20 mL of 28% ammonia solution.
2.2 Preparation of Ti4þ stock solution
A stock solution of Ti4þ was prepared by mixing titani-
um(IV) isopropoxide (TTIP; Aldrich, 97%) with triethanol-
amine (TEOA; Aldrich, 98%) under nitrogen atmosphere
at a molar ratio of TEOA/TTIP ¼ 2=1 to form a stable
complex of Ti4þ . To deposit a uniform TiO2 shell on the Au
nanoparticles, the hydrolysis reaction velocity of titanium
alkoxide needs to be decreased. Thus, TEOA was used as the
complexing agent to control the hydrolysis reaction velocity
of TTIP.19,20) A stable Ti4þ compound was prepared at room
temperature by adding the TEOA. Double distilled water
was then added to make 0.50 M Ti4þ solution. The stock
solution was prefiltered through PTFE membrane filters of
0.2 mm pore size prior to use.
2.3 Synthesis of Au/TiO2 core–shell nanoparticles
The concentrations of Ti4þ in the stock solution were
adjusted to 0.01– 0.3 mM. Then, 0.33 mL of the MUA–Au
colloid was added to 10 mL of the stock solution. The
resulting solution was placed into a screw-capped Pyrex
bottle and aged for 24 h at 80  C.
2.4 Characterization of Au/TiO2 nanoparticles
The morphology of the as-prepared Au/TiO2 composite
nanoparticles was examined using a transmission electron
microscope (JEM-2010, JEOL). To investigate the optical
property of the Au/TiO2 nanoparticles and to identify the
stability of the Ti4þ stock solution, UV–vis spectra were
taken using a UV–vis spectrophotometer (UV-2550, Shi-
madzu).
The change in crystallinity of the as-prepared Au/TiO2
nanoparticles according to heat treatment temperature was
evaluated by XRD analysis (D/Max 2005, Rigaku) with
Cu K
radiation at 40 kV and 100 mA. Au/TiO2 core–shell
colloid was sprayed on the quartz glass in order to make the
film and then was dried at 100  C. The crystalline size of the
particles was estimated using Scherrer’s equation.
3. Results and Discussion
Unlike other transition metal alkoxides, titanium alkox-
ides have a high rate of hydrolysis which is the principal
obstacle in the synthesis of core–shell nanoparticles with
titania shell. In this study, TTIP was used as a starting
material to coat TiO2 on the Au nanoparticles. TTIP was
mixed with TEOA as a complexing agent to control
hydrolysis reaction velocity. First of all, hydrolysis reac-
tivity was investigated at room temperature according to the
volume of TEOA for fixing the mixture ratio of TTIP and
TEOA. The mixture ratio of TEOA/TTIP was controlled at
0.9, 1.0, 1.5, and 2.0. Double distilled water was then added
to make a 0.50 M Ti4þ solution. Before the quantitative
analysis of the mixed solution, the occurrence of hydrolysis
2568
H.-W. KWON et al.
anatase
Intensity
20 40 60 80
2θ / degree
Fig. 1. XRD patterns of precipitates synthesized and sintered at 500  C for
3 h when ratio of TEOA/TTIP was 0.9.
2.0
(a) [TEOA]/[TTIP]=0.9
(b) [TEOA]/[TTIP]=1.0
1.5 (c) [TEOA]/[TTIP]=1.5
(d) [TEOA]/[TTIP]=2.0
Absorbance
1.0
0.5
0.0
200 300 400 500 600
Wavelength / nm
Fig. 2. UV–vis absorption spectrum of Ti4þ stock solution according to
molar ratio of TEOA/TTIP: (a) 0.9, (b) 1.0, (c) 1.5, and (d) 2.0.
reaction could be observed with naked eye. When the ratio
of TEOA/TTIP was 0.9, hydrolysis reaction started as soon
as water was added into the TEOA/TTIP mixed solution.
The TEOA/TTIP mixed solution became turbid. When the
ratio of TEOA/TTIP was more than 1.0, the occurrence of
hydrolysis reaction could not be observed with the naked
eye. Figure 1 shows the XRD pattern of the precipitates
synthesized and calcined at 500  C for 3 h when the ratio of
TEOA/TTIP was 0.9. The resulting precipitates were found
to have a pure anatase phase.
To quantify the hydrolysis reaction of the TTIP/TEOA
mixed solution, UV–vis spectroscopy was carried out.
Figure 2 shows the spectral changes associated with the
UV–vis absorption spectrum of the Ti4þ stock solution
according to the molar ratio of TEOA/TTIP. Inflection point
was observed at approximately 262 nm in the case where
the mixture ratios of TEOA/TTIP were 0.9 and 1.0, but
inflection points of 1.5 and 2.0 were also observed at
approximately 220 nm. Moreover, the behavior of UV–vis
spectra is different for different ratios of TEOA/TTIP (i.e.,
spectra will be different for the ratio above 1.5 and below
1.0). From this result, it was found that the stable ratio of
the TEOA/TTIP complex in water was more than 1.5.
The stable TEOA/TTIP complex was needed to deposit an
uniform TiO2 shell on the Au nanoparticles. In this study,
the ratio of TEOA/TTIP of 2.0 was fixed to strongly
Jpn. J. Appl. Phys., Vol. 46, No. 4B (2007)
(a) (b)
Fig. 3. TEM images of Au/TiO2 nanoparticles synthesized according to amount of Ti4þ in stock solution at 80  C: (a) 0.01, (b) 0.05,
and (c) 0.3 mM (300;000). Inset: single Au/TiO2 core–shell nanoparticle.
maintain the stability of the TEOA/TTIP complex solution
at room temperature.
To synthesize the Au/TiO2 nanoparticle with a core–shell
structure, we controlled the concentration of Ti4þ in the
stock solution. TEM images of Au/TiO2 particles were
obtained in the range of Ti4þ concentration from 0.01 to
0.3 mM at 80  C (as shown in Fig. 3). When the concen-
tration of Ti4þ was 0.01 mM, heterogeneous nucleation of
TiO2 on the surface of Au nanoparticles was obtained by the
hydrolysis of the Ti4þ stock solution. The separated colloidal
titania was not found and almost TiO2 was formed only on
the surface of Au nanoparticles as shown in the TEM
images. At 0.01 mM Ti4þ , Au/TiO2 composite nanoparticles
with a perfect core–shell structure were obtained and the
thickness of the TiO2 shell was about 10 nm, as shown in
Fig. 3(a). When the concentration of Ti4þ was 0.05 mM
[Fig. 3(b)], the Au/TiO2 nanoparticles were slightly coagu-
lated, but Au/TiO2 composite nanoparticles with a core–
shell structure were synthesized. Figure 3(c) shows the Au/
TiO2 composite nanoparticles prepared with 0.3 mM Ti4þ
solution. The Au nanoparticles were perfectly embedded in a
titania matrix. The perfect embedding was caused by
relatively high Ti4þ content as compared with that of Au
nanoparticles.
Figure 4 shows the absorption peaks of Au/TiO2 particles
synthesized according to the amount of Ti4þ in the stock
solution at 80  C. In this figure, the absorption peak of pure
Au nanoparticles was at 519 nm. At 0.05 mM Ti4þ in the
stock solution, the absorption peak appeared at 522 nm and
this peak was red-shifted to about 3 nm as compared with
that of the pure Au nanoparticle. It is found that the red-shift
of the absorption peak observed at 0.05 mM is caused by the
formation of titania shell with high refractive index on the
surface of gold particles. However, when the amount of Ti4þ
in the stock solution was changed between 0.05 and 0.1 mM,
the position of the UV–vis absorption peak was not red-
shifted. This result may be caused by the finding that any Au
nanoparticles no longer have a perfect core–shell structure at
the high concentration of Ti4þ but Au nanoparticles were
still separated the maintaning some distance in the TiO2
matrix, as shown in Fig. 3(c). The as-prepared titania shell
around the Au nanoparticles when the hydrothermal reaction
was completed was found to be amorphous from the TEM
diffraction pattern.
To investigate the effect of heat treatment temperature on
2569
H.-W. KWON et al.
(c)
50nm
5
(a) 0.1 mM - 522nm
(b) 0.05mM - 522nm
4 (c) 0.01mM - 521nm
(d) pure Au colloid-519nm
Absorbance
3
522nm
519nm
2
1
0
300 400 500 600 700 800
Wavelength / nm
Fig. 4. UV–vis absorption spectrum of Au/TiO2 particles according to
amount of Ti4þ in stock solution at 80  C.
the crystallinity of Au/TiO2 core–shell nanoparticles, an
Au/TiO2 composite nanoparticle film and a pure Au
nanoparticle film were calcined from 100 to 1000  C.
Figure 5 shows the XRD patterns of the pure Au nano-
particle film and the Au/TiO2 core–shell nanoparticle
(synthesized at ½Ti4þ  ¼ 1 mM) film. In this figure, the
peaks at 38 and 44 were assigned to the diffraction of the
(111) and (200) planes of gold and the peaks at 25.2 and 48
were assigned to the diffraction of the (101) and (004) planes
of TiO2 with an anatase structure.
From these XRD results, the crystallite sizes of the pure
Au and Au/TiO2 core–shell nanoparticles can be deduced
from the XRD line broadening using Scherrer’s equation.
Figure 6 shows the crystallite size changes of the pure Au
and Au/TiO2 core–shell nanoparticles. The crystallite size
of the pure Au nanoparticles rapidly increased from 13.9 to
70.2 nm up to 800  C, but that of the Au nanoparticles in the
Au/TiO2 core–shell nanoparticles slightly increased from
10.7 to 16.8 nm until 800  C. Therefore, the increase in the
Au nanoparticle crystallite size of the Au/TiO2 nanoparti-
cles is smaller than that in the pure Au nanoparticles because
Au nanoparticles were protected by the TiO2 shell. The
crystallite size of the TiO2 nanoparticles in the Au/TiO2
core–shell nanoparticles remains unaltered until 800  C
(average mean crystallite diameter  6.1 nm). However,
beyond 800  C, rapid increase in the crystallite size (40.8
nm) was recorded.
Jpn. J. Appl. Phys., Vol. 46, No. 4B (2007) H.-W. KWON et al.

(a) (b) Au
anatase

Intensity

Intensity
1000°C
1000°C 800°C
800°C 600°C
600°C
400°C
400°C
200°C 200°C

100°C 100°C

15 20 25 30 35 40 45 50 15 20 25 30 35 40 45 50
2θ / degree 2θ / degree

Fig. 5. XRD patterns of (a) pure Au nanoparticles and (b) Au/TiO2 core–shell nanoparticles (synthesized with ½Ti4þ  ¼ 1 mM) heated
at various temperatures.

(a) pure Au nanoparticle Acknowledgement

100
(b) Au in Au/TiO2 nanoparticle
This work was supported by the Eco-Techopia 21 Project
Size of Particles (nm)

(c) TiO2 in Au/TiO2 nanoparticle

80 (Korea Ministy of Environment) by Post BK21 program
from the Ministry of Education and Human Resources
60 Development.

40
20
0
200 400
Temperature ( C)
Fig. 6. Crystallite size changes of pure Au nanoparticles and Au/TiO2
core–shell nanoparticlse (synthesized with ½Ti4þ  ¼ 1 mM) according to
heat treatment temperature.
4. Conclusions
Au/TiO2 core–shell nanoparticles could be synthesized
by the hydrolysis of a TEOA/TTIP complex when the
temperature of hydrothermal reaction was at 80  C and the
concentration of Ti4þ was in the range of 0.01– 0.05 mM.
The thickness of the TiO2 shell on the Au nanoparticles was
about 10 nm. The peak position of the UV–vis absorption
spectrum of the Au/TiO2 core–shell nanoparticles was
shifted towards the red end of the spectrum by 3 nm as
compared with that of the Au nanoparticles, and it was
expected that the red shift was caused by the TiO2 shell.
When the pure Au nanoparticle film and the Au/TiO2 core–
shell nanoparticle film were heated at various temperatures,
the increase in the Au nanoparticle crystallite size in the Au/
TiO2 nanoparticles is smaller than that in the pure Au
nanoparticles because Au nanoparticles were protected by
the TiO2 shell.
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