Thin Solid Films 583 (2015) 135141

Contents lists available at ScienceDirect

Thin Solid Films

journal homepage: www.elsevier.com/locate/tsf

Solution plasma synthesis of Au nanoparticles for coating titanium

dioxide to enhance its photocatalytic activity
Yuki Nakasugi a, Genki Saito a, Toru Yamashita b, Norihito Sakaguchi a, Tomohiro Akiyama a,
a
b

Center for Advanced Research of Energy and Materials, Hokkaido University, Sapporo 060-8628, Japan
Faculty of Engineering, Hokkaido University, Sapporo 060-8628, Japan

a r t i c l e

i n f o

Article history:
Received 27 August 2014
Received in revised form 31 March 2015
Accepted 31 March 2015
Available online 6 April 2015
Keywords:
Gold
Nanoparticles
Coatings
Solution plasma
Photocatalysts

a b s t r a c t
A convenient method for coating titanium dioxide (TiO2) by Au nanoparticles (AuNPs) is demonstrated in solution plasma to improve the photocatalytic activity of TiO2. AuNPs from a metallic Au electrode were bonded to the
surface of a commercial TiO2 powder, which acted as a catalyst support, with the reaction taking place in an electrolyte solution. The effect of diverse plasma conditions on the size and productivity of the AuNPs was investigated initially to provide a reference in the absence of TiO2. At 290 V, partial plasma was attained, with only a weak
light emission surrounding the Au electrode. Conditions then evolved to full plasma, with a strong orange emission at 330 V. Partial or full status was maintained for 1 h at 300 and 400 V, respectively. At the transition to full,
the AuNP particle size increased from 3.72 to 6.09 nm and the productivity increased dramatically from 0.025 to
0.87 mg h1 mm2. Stronger plasma very efciently synthesized AuNPs, and therefore, it was adopted for further
study. AuNPTiO2 combinations were formed by applying 400 V to a TiO2-dispersed solution. In these experiments, TiO2 coated with AuNPs was synthesized; these combinations of AuNPTiO2 had 0.44 mol% of Au. The
photocatalytic activity of AuNPTiO2 was investigated by measuring the degradation of Rhodamine B (RhB).
Under UV irradiation, the AuNPTiO2 particles removed up to 95% of the dye in 70 min. Commercial TiO2 achieves
values closer to 85%. The results thus raise the possibility that solution plasma methods can be generalized as a
means for achieving catalysis-enhancing coatings.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Hybrid nanostructures such as metalsemiconductors [13], metal
magnets [4,5], and magnetsemiconductors [6,7] have been widely
investigated for their potential to improve the catalytic, physical, and
chemical properties compared to simpler systems. In particular, metal
and oxide semiconductor combinations have been studied with the
expectation of applications in optoelectronics, drug delivery, environmental monitoring, control of chemical processes, photocatalysis,
energy storage, and biomedical diagnosis applications [8,9].
In the eld of photocatalysis, nanoparticulate semiconductors have
been especially investigated because it is well known that the crystallinity and large specic surface area of semiconductor particles provide
essential advantages in photocatalytic reactions [10]. Good crystallinity
decreases the formation of electron traps, which might worsen the
photocatalytic efciency [11] and large specic surface area can provide
high number of active sites and provide large area for substance adsorption [12]. For the reasons mentioned above, nanosize semiconductor
particles have become very popular as photocatalysts with applications
studied ranging from the treatment and decomposition of organic
Corresponding author.
E-mail address: takiyama@eng.hokudai.ac.jp (T. Akiyama).

http://dx.doi.org/10.1016/j.tsf.2015.03.075
0040-6090/ 2015 Elsevier B.V. All rights reserved.

pollutants to hydrogen economy and water splitting [13,14]. In addition

to crystallinity and large surface area for the improvement of photocatalytic performance of oxide semiconductors such as TiO2 and ZnO, the
following methods have also attracted attention: coupling between
different semiconductors (e.g., TiO2/WO3 [15] and TiO2/SnO2 [16]),
combining noble metals with semiconductor photocatalysts (e.g., Ag/
TiO2 [17,18], Au/TiO2 [19], and Pt/TiO2 [20]), and introducing dopants
(e.g., oxygen defects [21], nitrogen [22], and sulfur [23]). In particular,
hybrid semiconductors coated with noble metal nanoparticles have
been investigated [24]. Excitons formed in the semiconductor move to
the metal nanoparticle layer and become trapped, improving the charge
separation [25]. In addition, light absorption by the oxides may be
enhanced [26]. Both of these effects facilitate redox reactions, thus
increasing the photocatalytic activity and light-harvesting efciencies
of semiconductor materials.
Gold is a unique noble metal in that its pure form is thermodynamically more stable than its oxides [27]. Methods discussed in the literature for the synthesis of Au coatings include, impregnation [28],
photodeposition [29], deposition precipitation [30], and solgel approaches [31]. However, ionic solutions are often required; for example,
using HAuCl4. Such media are strong oxidants and have high toxicity.
Additionally, low solubility limits mean that the above techniques
cannot be used to easily synthesize large amounts of AuNPs. Therefore,

Y. Nakasugi et al. / Thin Solid Films 583 (2015) 135141

2. Experiment
2.1. Synthesis of AuNPs
Conditions within the plasma have a strong inuence on particle
diameter and the yield of products [39]. To establish the optimal experimental arrangement, plasma behaviors were varied systematically. The
main laboratory setup consisted of two electrodes in a glass cell with a
capacity of 300 ml, as shown in Fig. 1. A platinum wire served as the
anode (length: 1000 mm, diameter: 0.5 mm, purity 99.98 mass%;
Nilaco). This was bent into a half-round mesh. The Au wire functioned
as the cathode (diameter: 1.0 mm, purity: 99.99 mass%; Sanwakinzoku
Corp.). The upper and lower parts of Au wire were covered with an
electrically insulated quartz tube in order to maintain the length of
the exposed portion constant at 10 mm. Hence, only the central section
was actually involved in the electrochemistry. The electrolyte solution
was 0.01 M NaOH, and the electrolysis runs were performed under a
given stable power supply (ZX800H, Takasago). The solution temperature was recorded every 5 s by positioning a polymer-coated thermistor
at a depth of 10 mm (Ondotori TR-71Ui, T&D).
The following procedure was adopted in order to produce the AuNPs.
First, the electrolyte was pre-warmed at 60 5 C since it was found that
this signicantly reduced the time required for accumulation. Subsequently, the potential was increased by 0.5 V s1 until the maximum
values of 300 V (Case 1) and 400 V (Case 2) were obtained. The levels
were then xed for 1 h. Current and temperature were recorded during
this process. The synthesized nanoparticles were characterized by transmission electron microscopy (TEM, JEOL JEM-2010F). A 300 kV microscope (FEI Titan) was employed for high-resolution TEM (HRTEM)
observations. This microscope was equipped with a monochromator
and a CEOS image Cs-corrector. The morphology of the Au electrode
surface was investigated post hoc by using a eld-emission scanning
electron microscope (FE-SEM, JEOL JSM-7001FA). The nanoparticle size
was determined from the TEM images on the basis of sample number.
2.2. Synthesis of AuNPTiO2
To fabricate the AuNPTiO2 combination, AuNPs were synthesized
by using solution plasma with TiO2 (P25, Degussa), which is added to

Thermistor

D.C.
Power source
0 650 V
- + PtAnode
wire
(0.5 mm )

10 mm
Quartz tube
Cathode
Au wire
(1 mm )

10 mm

it is desirable that alternate pathways be developed for synthesizing

AuNP coatings.
Among several strategies available for the synthesis of nanoparticles,
plasma generation in solution is especially attractive [32,33]. It holds the
potential for large-scale production, and it does not require any gas
supply. The plasma technique is suitable for the synthesis of virtually
all conductive metals and alloys [34]. AuNPs have been generated by
this method, but typically by using ionizing solutions [3537]. There is
a contrasting approach in which nanoparticles are formed from a solid
electrode within the solution plasma. The method may be considered
relatively safe because AuNPs result directly from the solid material.
High yields can be expected because the electrode provides a large
mass reservoir. Toriyabe et al. have reported the formation of AuNPs
in solution plasma [38] but report of laboratory synthesis of composite
materials of metal nanoparticles and semiconductor powders via solution plasma could not be found.
In the present study, we produced AuNPs via solution plasma
methods, and the effect of diverse plasma conditions on the size and
productivity was investigated initially in the absence of TiO2 to provide
the optimal condition, which indicates that numerous particles were
synthesized in the nm range. Subsequently, we produced them under
the optimal condition using a TiO2 powder dispersed in solution as the
main catalytic support. AuNPs, generated from a Au rod functioning as
an electrode within the plasma medium, were attached to the surface
of the catalyst support. Our goal is to provide a convenient one-step
synthesis of AuNP-supported TiO2.

Camera

136

300 mL 0.01 M NaOH

with/without TiO2 particles
Fig. 1. Schematic diagram of the experimental apparatus, containing a platinum wire
anode of length 1000 mm and diameter 0.5 mm and a Au wire cathode of diameter
1 mm; 10 mm of the cathode wire was exposed partially. The electrolyte used was
0.01 M NaOH solution, with/without TiO2 particles.

the electrolyte as a catalysis support. Before applying the voltage,

100 mg of TiO2 was added to the 0.01 M NaOH solution and dispersed
by supersonic waves. The voltage was xed at 400 V for 1 h. The products were later collected by centrifugation and rinsed several times in
deionized water with an ultrasonic cleaner. The microstructure of the
products was investigated by TEM. An energy-dispersive X-ray
spectrometer (EDS) determined the extent of AuNP coating on TiO2.
2.3. Measurement of photocatalytic activity
The photocatalytic capability of the products was determined by
measuring the rate of degradation of RhB in an aqueous solution
under UV irradiation. The lamp in these experiments was positioned
12 cm away from the suspension. Its peak wavelength () was
357 nm, with a net output of 30 W. A suspension was prepared by
adding 20 mg products into 2 105 M RhB of 100 ml. Before UV irradiation, the suspension was magnetically stirred in the dark for 30 min
to reach adsorption equilibrium on the catalytic surface. The suspension
was irradiated by the UV source under continuous stirring at room temperature. Two electric fans were used to avoid any temperature increase
during the procedure. After initiation of the reaction by the irradiation,
5 ml of the suspension was sampled every 10 min. Centrifugal separation was conducted to remove the products completely. UVvisible
absorption spectra of the centrifuged solutions were recorded using a
commercial photometer (USB2000+, Ocean Optics).
3. Results and discussion
3.1. Synthesis of AuNPs at optimal experimental conditions
The size and productivity of the nal product in the case of nickel
and titanium systems increased when the plasma condition was
changed from partial to full plasma showing a strong emission by
increasing the voltage applied [39,40]. The effect on AuNPs was not

Y. Nakasugi et al. / Thin Solid Films 583 (2015) 135141

137

500

B (400V)

Generation of the infrared radiation

Generation of the plasma
400

Case 2; 400 V

Cell voltage (V)

B
A

300

Case 1; 300 V
200

A (300V)

Rate of applied voltage; 0.5 V s-1

100

10

20

30

40

50

60

70

80

Time (min)
Fig. 2. (Left) Cell voltage histories in the electrolysis solutions, with an application rate of 0.5 V s1. The voltage was xed at 300 or 400 V for 1 h. (Right) Photographs of electrodes during
plasma electrolysis. Emissions in (B) had more beams than (A).

investigated in the previous studies. Hence the relevant results are

reported here in the present work. Fig. 2 displays cell voltage histories
observed during the synthesis of AuNPs. When the potential was
ramped at a rate of 0.5 V s 1, the partial plasma occurred at about
290 V. Its intensity increased with the applied voltage because ionization of the chemical species involved was enhanced. The photograph
(A) in Fig. 2 shows an electrode supporting a partial plasma with a voltage of 300 V maintained for 1 h. This will be referred to as Case 1 for
AuNP generation. When the voltage continued rising over 300, the
plasma transitioned to its full state, with a strong orange emission
setting in at 330 V. This situation is illustrated in photograph (B). Case 2
involved steady full plasma conditions, driven by 400 V over 1 h.
TEM observation of AuNPs was conducted to investigate the particle
morphology and size. The surface of the Au electrode was characterized
after the experiment by the SEM. The results are summarized in Fig. 3.

TEM of the product

Applied at 300 V
(120)

The AuNPs were mainly spherical, and the smallest size was less than
2 nm. Clearly surface tension effects have caused the molten metal to
adopt a spherical shape. The high resolution TEM images shown in
Fig. 4 indicate that both polycrystalline material and single crystals
were formed. Additionally, the polycrystalline nanoparticles contained
multitwin-particles (MTPs) of decahedral geometry [4143]. The formation of single crystals, nanotwins, and MTPs as decahedrons or icosahedrons has been reported in previous solution plasma [44]. As particle
size decreases, defect structures such as MT become thermodynamically
stable. In the experiments conducted here with relatively large particles,
a general spectrum of polycrystalline materials resulted. Both individual
twins and MTPs were created. By contrast, small diameter particles
tended to occur as single crystals.
The mean number diameter of the products was measured based on
TEM imagery as shown in Fig. 5. At Case 1, the particle size was 3.72

Applied at 400 V

(220)

(110)

(120)
(111)
(100)

(111)

(110)

(220)

(222)

10 nm

SEM of the Au wires

10 nm

50

Fig. 3. TEM of the product (left) and SEM of the Au wire surface after the experiments (right). The products were mainly spherical. The smallest particle size was less than 2 nm in
both cases.

138

Y. Nakasugi et al. / Thin Solid Films 583 (2015) 135141

(a)

(b)

(c)

Fig. 4. HR-TEM images of AuNPs with single crystalline (a), twin-induced particle (b), and multitwin-particles of decahedral conguration (c). Results are for 300 V. The dashed line shows
a twin boundary. The particles with relatively small diameters tended to be synthesized as single crystals.

1.27 nm, and at Case 2, it was 6.09 2.07 nm. Because the nanoparticle
formation occurs in the solution plasma by the local concentration of
electric current, more nanoparticles with larger diameters are synthesized at higher current densities [45]. Table 1 lists the relevant experimental parameters and results. The electric current observed in Case 2
was 0.357 A, higher than that observed in Case 1, which is 0.190 A. As
a result, when a high voltage was applied, the surface temperature of
the electrode became high enough to radiate the infrared. This explains
the observed strong emission in the red-yellow portion of the visible
wavelength ranges [39,40]. The electrode surfaces were studied after
electrolysis with respect to their morphology. As shown in Fig. 3 for
Case 1, holes and pitting were apparent on the electrode surface. Current had clearly been concentrated in certain localities and the AuNPs
formed at these points. In Case 2, the surface was very rough because
the temperature of electrode surface became higher. Thus, a reduced
current density with lower applied voltage seems to be more effective
in the formation of smaller particles.
The amount of product was evaluated by weighing the electrodes
before and after key experiments. As shown in Table 1, the applied voltage affected not only the size of the products, but also the process yield.
In Case 2, the product accumulation was 0.87 mg h1 mm2, a considerably larger rate than the value 0.025 mg h1 mm2 obtained in Case 1.
The plasma transitioned to its full state by 400 V, so that numerous

35

Case 1 (300 V); partial plasma

Mean diameter: 3.72 nm
N = 582

30
25
20

particles were synthesized in the nm range. The higher potential level

therefore offers signicant advantages in the coating procedure.
3.2. Particle morphology
The AuNPs were formed by applying 400 V in the 0.01 M NaOH
solution by adding TiO2 as a catalyst support. TEM images (left) and
photographs (right) of the combined products are provided in Fig. 6.
Their color changed from white to burgundy when the AuNPs attached
to TiO2. The surface plasmon resonance is observed when Au attains the
nanoscale [46]. Although the resonance wavelength varies with size and
shape, spherical structures usually display a peak at around 550 nm
[47]. As a result the color has changed to a red tone not seen in the
bulk. Because red AuNPs were distributed over the surface of TiO2, the
appearance of the product was altered; this can be seen in the gure.
Moreover, blue shades appeared when the nanoparticles agglutinated.
There is thus a possibility that AuNPs were deposited on TiO2 in dispersion as opposed to aggregation. In fact, our TEM images show that
AuNPs were supported on TiO2 in dispersion. This suggests the possibility of attachment in droplet state prior to solidication. The structure of
the products before/after AuNP coating was characterized by using XRD
(Fig. 7). The XRD pattern of the un-coated products can be indexed according to anatase- and rutile-type TiO2, which shows that the crystalline structure was composed of them in a ratio of 7 to 1. In contrast,
AuNPTiO2 was composed of not only TiO2 but also Au. These results
show that the plasma eld did not affect to the crystal structure of
TiO2. Fig. 8 displays an EDS spectrum of the product, indicating the presence of Au. The AuNPs appear to have stabilized on the TiO2 interface at
0.44 mol%.

Frequency (%)

15

3.3. Photocatalytic performance of AuNPTiO2

10
5
0
14

Case 2 (400 V); full plasma

Mean diameter: 6.09 nm
N = 618

12
10

8
6
4
2

The photocatalytic performance of AuNPTiO2 was evaluated by the

photodegradation of RhB (initial concentration, 2 105 M). A selection of results is presented in Fig. 9. RhB was decomposed by 30 W UV
irradiation in the presence of baseline and product photocatalysts,
which were 20 mg of TiO2 and AuNPTiO2 powder, respectively. The
degradation rate of the dye compound was calculated from a decrease
in the intensity at the 553 nm absorption peak, which is the major
feature of the attendant spectrum. When pure TiO2 was used as
the photocatalyst, RhB showed about 85% degradation in 70 min. The

0
1

10

11

12

13

Particle size (nm)

Fig. 5. Particle size-distributions of the products, measured from TEM images of the
products, together with the mean diameter based on number and the sample number N.
The mean number diameter of the products synthesized by full plasma was slightly bigger
than that of partial plasma.

Table 1
Summary of the experimental parameters and results.

Case 1
Case 2

Maintained
voltage (V)

Mean
current (A)

Mean number
diameter (nm)

Production
amount (mg)

300
400

0.190
0.357

3.72 1.27
6.09 2.08

0.80
27.4

Y. Nakasugi et al. / Thin Solid Films 583 (2015) 135141

TEM images of Products

139

TiO2

Photographs of Products

10 mm

20 nm

10 mm

AuNP-TiO2

20 nm

Au

Fig. 6. TEM images (left) and photographs (right) of the products. Color became purple because of the surface plasmon resonance of AuNPs. (For interpretation of the references to color in
this gure legend, the reader is referred to the web version of this article.)

Anatase: 86.5 %

Intensity (arb.unit)

Rutile: 12.8%
Au: 0.7 %

AuNP
-TiO2

TiO2
10

20

30

40

50

60

70

80

90

Degree, 2(, CuK)

Fig. 7. XRD patterns of the products before and after Au coating. The XRD pattern of the uncoated products can be indexed according to anatase- and rutile-type TiO2. In contrast,
AuNPTiO2 was composed of not only TiO2 but also Au.

the UV cannot be excluded. Multielectron reduction of oxygen represents yet another potential contributing factor, since the nanoparticles
act as an electron reservoir. The energy change for the multielectron reduction of oxygen is more positive than for the single-electron counterpart [49]. As a result oxygen reduction, which is a common ratedetermining step in photocatalytic reaction [50], might be more
progressed. Any or all of the above processes may have played a role
in the augmentation of photocatalytic activity documented here for
AuNP coated TiO2.
4. Conclusion
We have synthesized AuNPs by applying a solution plasma technique, and we then coated the AuNPs onto TiO2 in order to investigate
the effects on the photocatalytic behavior of TiO2. To optimize the
experimental conditions such that AuNPs of small diameters were
efciently generated, we studied the inuence of different plasma conditions on the size and productivity of the AuNPs. In the case of partial
plasma with weak light emission at 300 V, the particle size was 3.72
1.27 nm. Productivity was determined to be 0.025 mg h1 mm 2.

Intensity (arb.unit)

degradation became about 95% in the presence of AuNPTiO2 over the

same period.
There are several possible reasons for the improved photocatalytic
activity afforded by the AuNP-coating procedure. The surface area may
have been increased by the AuNPs, enhancing the contact with the
dye substrate. It is also conceivable that electrons released by UV irradiation are transferred from TiO2 to AuNPs because of their different work
functions [48]. Recombination of the electrons and the corresponding
positive-holes was likely prevented by a distance effect. Therefore,
charge separation was increased. A third possibility is that the visible
tail of the ultraviolet spectrum was involved. AuNPs have a spectral
peak at around 550; therefore, the possibility of absorption outside

Ti

Au 0.44 mol %

O
Ti
Ti

Au Au
0

Energy (keV)
Fig. 8. EDS spectrum of AuNPTiO2, in which Au was supported at 0.44 mol%.

140

Y. Nakasugi et al. / Thin Solid Films 583 (2015) 135141

120
No UV-irradiation
100

Ct/C0 (%)

80
Sample mass; 20 mg
60

UV light; 30W

Solution; 2 x10-5 M RhB

40
AuNP-TiO2

20

TiO2

0
0

10

20

30

40

50

60

70

UV - light exposure time (min.)

120

120
No UV-irradiation

100

Sample mass; 20 mg
UV light; 30W
Solution; 2 x10-5 M RhB

60

80
60
Intensity (arb.unit)

80

40

AuNP-TiO2

20

TiO2

Ct/C0 (%)

100

Ct/C0 (%)

Fluorescent light; 30W

Solution; 2 x10-6 M RhB

40
20

200

400
600
Wavelength (nm)

800

0
0

10

20

30

40

50

70 0

60

10

20

30

40

50

60

70

UV - light exposure time (min.)

120

Fluorescent light; 30W

Solution; 2 x10-6 M RhB

100

60
Intensity (arb.unit)

Ct/C0 (%)

80

40
20

200

300

400
500
600
Wavelength (nm)

700

800

0
0

10

20

30

40

50

60

70

UV - light exposure time (min.)

Fig. 9. Degradation of RhB by different catalysts under UV-irradiation. The vertical line shows the degradation rate of RhB. Decomposition of RhB using AuNPTiO2 took place earlier than in
the case of pure TiO2.

In contrast, for full plasma characterized by a strong orange emission

(400 V), 6.09 2.07 nm particles were generated 0.87 mg h1 mm2.
AuNPTiO2 was formed by synthesizing AuNPs in an electrolyte containing TiO2 as the catalysis support. The AuNPs coated the TiO2 at
0.44 mol%. The photocatalytic activity of TiO2 was signicantly improved
by AuNP coating because of the increase in the TiO2 surface area and
charge separation. The latter is attributable to a difference in the work
function between the two materials. Our hybrid semiconductor AuNP
TiO2 demonstrates an efcient catalytic performance. This implies commercialization potential in the elds of water purication, remediation

of air pollution, energy conversion devices, biofunctionalized materials,

and infrared-emitting/detecting devices.
Acknowledgment
A part of this work was conducted at Hokkaido University, supported by the Nanotechnology Platform Program of the Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT). We
especially wish to thank Mr. Kenji Ohkubo and Mr. Ryo Ota for their
great technical assistance and helpful suggestions.

Y. Nakasugi et al. / Thin Solid Films 583 (2015) 135141

References
[1] A.E. Saunders, I. Popov, U. Banin, Synthesis of hybrid CdSAu colloidal nanostructures,
J. Phys. Chem. B 110 (2006) 25421.
[2] E. Elmalem, A.E. Saunders, R. Costi, A. Salant, U. Banin, Growth of photocatalytic
CdSePt nanorods and nanonets, Adv. Mater. 20 (2008) 4312.
[3] H. Kim, Y.J. Choi, Y.H. Kim, H.H. Park, One-step synthesis of Pt nanoparticles
incorporated direct-patternable SnO2 nanocomposite thin lms, Surf. Coat. Technol.
231 (2013) 385.
[4] Y. Li, Q. Zhang, A.V. Nurmikko, S. Sun, Enhanced magnetooptical response in
dumbbell-like AgCoFe2O4 nanoparticle pairs, Nano Lett. 5 (2005) 1689.
[5] L. Zhang, Y.H. Dou, H.C. Gu, Synthesis of AgFe3O4 heterodimeric nanoparticles, J.
Colloid Interface Sci. 297 (2006) 660.
[6] H.Y. Lin, Y.F. Chen, J.G. Wu, D.I. Wang, C.C. Chen, Carrier transfer induced
photoluminescence change in metalsemiconductor coreshell nanostructures,
Appl. Phys. Lett. 88 (2006) 161911.
[7] K.W. Kwon, M. Shim, -Fe2O3/IIVI sulde nanocrystal heterojunctions, J. Am.
Chem. Soc. 127 (2005) 10269.
[8] M. Ahmad, L. Gan, C. Pan, J. Zhu, Controlled synthesis and methanol sensing
capabilities of Pt-incorporated ZnO nanospheres, Electrochim. Acta 55 (2010) 6885.
[9] X. Liang, B. Xu, S. Kuang, X. Wang, Multi-functionalized inorganicorganic rare earth
hybrid microcapsules, Adv. Mater. 20 (2008) 3739.
[10] G. Tian, H. Fu, L. Jing, B. Xin, K. Pan, Preparation and characterization of stable
biphase TiO2 photocatalyst with high crystallinity, large surface area, and enhanced
photoactivity, J. Phys. Chem. C 112 (2008) 3038.
[11] J. Ovenstone, Preparation of novel titania photocatalysts with high activity, J. Mater.
Sci. 36 (2001) 1325.
[12] Z. Zhang, C.C. Wang, R. Zakaria, J.Y. Ying, Role of particle size in nanocrystalline
TiO2-based photocatalysts, J. Phys. Chem. B 102 (1998) 10871.
[13] M.R. Hoffmann, S.T. Martin, W. Choi, D.W. Bahnemann, Environmental applications
of semiconductor photocatalysis, Chem. Rev. 95 (1995) 69.
[14] A. Mills, S.L. Hunte, An overview of semiconductor photocatalysis, J. Photochem.
Photobiol. A Chem. 108 (1997) 1.
[15] S. Higashimoto, M. Sakiyama, M. Azuma, Photoelectrochemical properties of hybrid
WO3/TiO2 electrode. Effect of structures of WO3 on charge separation behavior, Thin
Solid Films 503 (2007) 201.
[16] K. Vinodgopal, I. Bedja, P.V. Kamat, Nanostructured semiconductor lms for
photocatalysis. Photoelectrochemical behavior of SnO2/TiO2 composite systems and
its role in photocatalytic degradation of a textile Azo dye, Chem. Mater. 8 (1996) 2180.
[17] T. Hirakawa, P.V. Kamat, Photoinduced electron storage and surface plasmon
modulation in Ag@TiO2 clusters, Langmuir 20 (2004) 5645.
[18] O. Akhavan, Lasting antibacterial activities of AgTiO2/Ag/a-TiO2 nanocomposite
thin lm photocatalysts under solar light irradiation, J. Colloid Interface Sci. 336
(2009) 117.
[19] Y. Tian, T. Tatsuma, Mechanisms and applications of plasmon-induced charge
separation at TiO2 lms loaded with gold nanoparticles, J. Am. Chem. Soc. 127
(2005) 7632.
[20] A. Furube, T. Asahi, H. Masuhara, H. Yamashita, M. Anpo, Direct observation of a
picosecond charge separation process in photoexcited platinum-loaded TiO2 particles
by femtosecond diffuse reectance spectroscopy, Chem. Phys. Lett. 336 (2001) 424.
[21] T. Ihara, M. Miyoshi, M. Ando, S. Sugihara, Y. Iriyama, Preparation of a visible-lightactive TiO2 photocatalyst by RF plasma treatment, J. Mater. Sci. 36 (2001) 4201.
[22] M. Miyauchi, A. Ikezawa, H. Tobimatsu, H. Irie, K. Hashimoto, Zeta potential and
photocatalytic activity of nitrogen doped TiO2 thin lms, Phys. Chem. Chem. Phys.
6 (2004) 865.
[23] T. Umebayashi, T. Yamaki, H. Itoh, K. Asai, Band gap narrowing of titanium dioxide
by sulfur doping, Appl. Phys. Lett. 81 (2002) 454.
[24] Q. Wang, B. Geng, S. Wang, ZnO/Au hybrid nanoarchitectures: wet-chemical
synthesis and structurally enhanced photocatalytic performance, Environ. Sci.
Technol. 43 (2009) 8968.
[25] R. Costi, A.E. Saunders, E. Elmalem, A. Salant, U. Banin, Visible light-induced charge
retention and photocatalysis with hybrid CdSeAu nanodumbbells, Nano Lett. 8
(2008) 637.

141

[26] K. Awazu, M. Fujimaki, C. Rockstuhl, J. Tominaga, H. Murakami, Y. Ohki, N. Yoshida,

T. Watanabe, A plasma photocatalyst consisting of silver nanoparticles embedded in
titanium dioxide, J. Am. Chem. Soc. 130 (2008) 1676.
[27] M. Haruta, Novel catalysis by gold: a modern alchemy, J. Vac. Soc. Jpn. 51 (2008)
721.
[28] W.C. Li, M. Comotti, F. Schuth, Highly reproducible syntheses of active Au/TiO2
catalysts for CO oxidation by depositionprecipitation or impregnation, J. Catal.
237 (2006) 190.
[29] S.C. Chan, M.A. Barteau, Preparation of highly uniform Ag/TiO2 and Au/TiO2
supported nanoparticle catalysts by photodeposition, Langmuir 21 (2005) 5588.
[30] N.S. Patil, B.S. Uphade, D.G. McCulloh, S.K. Bhargava, V.R. Choudhary, Styrene
epoxidation over gold supported on different transition metal oxides prepared by
homogeneous depositionprecipitation, Catal. Commun. 5 (2004) 681.
[31] R.S. Sonawane, M.K. Dongare, Solgel synthesis of Au/TiO2 thin lms for photocatalytic
degradation of phenol in sunlight, J. Mol. Catal. A Chem. 243 (2006) 68.
[32] G. Saito, S. Hosokai, M. Tsubota, T. Akiyama, Synthesis of copper/copper oxide
nanoparticles by solution plasma, J. Appl. Phys. 110 (2011) 023302.
[33] P. Pootawang, N. Saito, O. Takai, S.Y. Lee, Synthesis and characteristics of Ag/Pt
bimetallic nanocomposites by arc-discharge solution plasma processing,
Nanotechnology 23 (2012) 395602.
[34] G. Saito, S. Hosokai, T. Akiyama, Synthesis of ZnO nanoowers by solution plasma,
Mater. Chem. Phys. 130 (2011) 79.
[35] J. Hieda, N. Saito, O. Takai, Size-regulated gold nanoparticles fabricated by a
discharge in reverse micelle solutions, Surf. Coat. Technol. 202 (2008) 5343.
[36] S.M. Kim, G.S. Kim, S.Y. Lee, Effects of PVP and KCl concentrations on the synthesis of
gold nanoparticles using a solution plasma processing, Mater. Lett. 62 (2008) 4354.
[37] S.P. Cho, M.A. Bratescu, N. Saito, O. Takai, Microstructural characterization of gold
nanoparticles synthesized by solution plasma processing, Nanotechnology 22
(2011) 455701.
[38] Y. Toriyabe, S. Watanabe, S. Yatsu, T. Shibayama, Controlled formation of metallic
nanoballs during plasma electrolysis, Appl. Phys. Lett. 91 (2007) 041501.
[39] Y. Nakasugi, G. Saito, T. Yamashita, T. Akiyama, Synthesis of nonstoichiometric
titanium oxide nanoparticles using discharge in HCl solution, J. Appl. Phys. 115
(2014) 123303.
[40] G. Saito, S. Hosokai, M. Tsubota, T. Akiyama, Nickel nanoparticles formation from solution plasma using edge-shielded electrode, Plasma Chem. Plasma Process. 31
(2011) 719.
[41] S. Ino, S. Ogawa, Multiply twinned particles at earlier stages of gold lm formation
on alkalihalide crystals, J. Phys. Soc. Jpn. 22 (1967) 1365.
[42] H. Hofmeister, Habit and internal structure of multiply twinned gold particles on
silver bromide lms, Thin Solid Films 116 (1984) 151.
[43] M. Mitome, Y. Tanishiro, K. Takayanagi, On the structure and stability of small metal
particles: high-resolution UHV electron microscope study, Atoms Mol. Clust. 12
(1989) 45.
[44] X. Hu, S.P. Cho, O. Takai, N. Saito, Rapid synthesis and structural characterization of
well-dened gold clusters by solution plasma sputtering, Cryst. Growth Des. 12
(2012) 119.
[45] G. Saito, S. Hosokai, T. Akiyama, S. Yoshida, S. Yatsu, S. Watanabe, Size-controlled Ni
nanoparticles formation by solution glow discharge, J. Phys. Soc. Jpn. 79 (2010)
083501.
[46] H. Yu, M. Chen, P.M. Rice, S.X. Wang, R.L. White, S. Sun, Dumbbell-like bifunctional
AuFe3O4 nanoparticles, Nano Lett. 5 (2005) 379.
[47] Y. Tian, H. Liu, G. Zhao, T. Tatsuma, Shape-controlled electrodeposition of gold
nanostructures, J. Phys. Chem. B 110 (2006) 23478.
[48] H. Zhang, G. Chen, D.W. Bahnemann, Photoelectrocatalytic materials for environmental
applications, J. Mater. Chem. 19 (2009) 5089.
[49] R. Abe, H. Takami, N. Murakami, B. Ohtani, Pristine simple oxides as visible light
driven photocatalysts: highly efcient decomposition of organic compounds over
platinum-loaded tungsten oxide, J. Am. Chem. Soc. 130 (2008) 7780.
[50] M. Ahmad, S. Yingying, A. Nisar, H. Sun, W. Shen, M. Wei, J. Zhu, Synthesis of
hierarchical ower-like ZnO nanostructures and their functionalization by Au
nanoparticles for improved photocatalytic and high performance Li-ion battery
anodes, J. Mater. Chem. 21 (2011) 7723.