Journal of Alloys and Compounds 662 (2016) 84e88

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Template free preparation of TiO2/C coreeshell hollow sphere for high

performance photocatalysis
Yan Zhuang*, Jianhua Sun, Mingyun Guan
School of Chemistry & Chemical Engineering, Jiang Su University of Technology, NO. 1801 Zhongwu Avenue, Changzhou City, Jiangsu Province, PR China

a r t i c l e i n f o a b s t r a c t

Article history: TiO2/C coreeshell hollow sphere has been prepared successfully and template-freely by a traditional
Received 5 July 2015 hydrothermal reaction and followed by solution method and annealing under Ar atmosphere. The carbon
Received in revised form core serves as the acceptor of photo-generated electrons and stops the electronehole pairs from
27 July 2015
recombination without loss of the light adsorption of the TiO2 photocatalyst. The as-prepared composite
Accepted 9 August 2015
performs a slight red shift and higher absorbance than that of pure TiO2, resulting in higher photo-
Available online 12 August 2015
catalytic activity. The TiO2/C coreeshell hollow sphere presents excellent photocatalytic activity that the
Rhodamine B (RhB) can be photo-degraded by more than 90% under two hours' UV irradiation
Keywords:
TiO2
comparing to 70% of pure TiO2 hollow sphere. Furthermore, the kinetic rate of TiO2/C coreeshell hollow
Hollow sphere sphere is twice as high as the pure TiO2. The results suggest that the as-prepared TiO2/C coreeshell
Photocatalysis hollow sphere has potential application in waste water treatment industry.
Photocatalytic activity © 2015 Elsevier B.V. All rights reserved.
Core/shell

1. Introduction
Photocatalysis has attracted increasing interest over the last
decades due to its extensive applications spanning from many
fields such as: solar fuel production [1,2], water splitting [3,4],
photo-degradation of pollutants, and catalysis of other chemical
reactions in contaminated water [5,6]. The photocatalytic operation
usually involves photoactive semiconductors, mostly the ones,
which consist of metal-based semiconductors like ZnO [7], TiO2 [8],
Fe2O3 [9], CdS [2], and many others. Of these large amount
transition-metal oxides, titanium dioxide (TiO2) has gained
particular attraction as a wide band gap semiconductor due to its
wide-spread applications in many chemical and physical related
fields [10e13].
Recently, inorganic materials with specific structural features
have attracted much attention because of intriguing physical
properties caused by their unusual sizes and shapes [14,15]. Among
them, the spherical hollow structures certainly provide advanta-
geous features, such as a low density and a large surface area, so
that they would have potential applications in photocatalysis [16].
Furthermore, recent progress shows that hollow TiO2 spheres
present enhanced performance in photocatalysis and photovoltaics
* Corresponding author.
E-mail address: ya_zhuang@126.com (Y. Zhuang).
due to their light scattering, organic adsorption, and porous char-
acteristics [17,18].
For efficient photocatalysis, the internal recombination rate of
the charge carriers should be sufficiently long to allow electro-
nehole pairs migration to the surface of the catalyst, in order to
perform the desired reaction [19]. A normally used route to stop the
recombination of the electronehole pairs is to coat a thin layer
around the photocatalyst. However, the carbon coating will
decrease the light absorption and also the contact between pho-
tocatalyst and contaminant molecules, which will have great side
effect on the activity of the photocatalyst. Consideration of this
problem, how to resist the recombination of electronehole pairs
while keeping high photocatalytic activity is the motivation of this
work.
In this work, the TiO2/C coreeshell hollow sphere has been
synthesized by the traditional hydrothermal reaction and followed
by solution method and annealing under Ar atmosphere. The car-
bon core serves as the acceptor of photo-generated electrons and
stops electronehole pairs from recombination without loss of the
light adsorption of the TiO2 photocatalyst. As a result, the as-
prepared TiO2/C coreeshell hollow sphere composite shows a
slight red shift and higher absorbance than that of pure TiO2 hollow
sphere, resulting in higher photocatalytic activity. The TiO2/C cor-
eeshell hollow sphere photocatalyst owns excellent photocatalytic
activity that the RhB can be photo-degraded by more than 90%
under two hours' UV irradiation and the rate of reaction kinetics is

http://dx.doi.org/10.1016/j.jallcom.2015.08.067
0925-8388/© 2015 Elsevier B.V. All rights reserved.
 Y. Zhuang et al. / Journal of Alloys and Compounds 662 (2016) 84e88 85

twice as high as the pure TiO2, suggesting that the as-prepared

TiO2/C coreeshell hollow sphere is very promising in waste water
treatment application.

2. Experiment details

The carbon hollow sphere was synthesized by a traditional hy-

drothermal reaction [20,21]. Typically, 6 g glucose and 50 mg so-
dium dodecyl sulfate (SDS) were dissolved in 40 mL distilled water
under stirring for more than 15 min, which was then transferred


into a 50 mL Teflon-lined autoclave and heated at 180 C for 8 h.
After cooled down to room temperature, the brown product was
cleaned with distilled water and alcohol for several times and


vacuum dried at 80 C for more than 12 h.
TiO2/C coreeshell hollow sphere was prepared as following:
100 mg carbon hollow sphere was dispersed in 20 mL alcohol under
strong stirring. Then different amount of tetrabutyl titanate (TBOT)
(0.2, 1, and 5 mL) was added into the mixed solution to prepare
TiO2/C composite with different TiO2 content. After being stirred for
10 h at room temperature the products were washed with distilled
water and alcohol for several times and vacuum dried at 80
C for


more than 12 h before annealed in Ar atmosphere at 600 C for 3 h.
Scheme 1. Schematic diagram illustrates the preparation of TiO2/C hollow sphere and
The products are designated as TiO2/C-0.2, TiO2/C-1, and TiO2/C-5. its photocatalytic activity enhancement mechanism.
Pure TiO2 was obtained by annealed the TiO2/C-1 in air at 600
C for
3 h. Pure carbon sphere was obtained by annealed the hydrother-


mal product in Ar atmosphere at 600 C for 3 h. the enhancement mechanism in photocatalytic activity is shown in
The morphologies of the samples were observed by field Scheme 1. When the UV light irradiating to the photocatalyst, large
emission scanning electron microscope (FESEM, JSM-6700) and amount photo-generated electrons and holes will produced. The
Transmission electron microscope (TEM, Philips tecnai 12). The generated electrons will transfer to the conductive band (CB) and
crystallographic structures of the samples were characterized by X- the holes left at the valance band (VB). Generally, the generated
ray diffraction (XRD, X'pert Pro) with Cu ka radiation electrons and holes will recombine soon and no active charge
(l ¼ 0.15406 nm) in the 2 theta angle of 20e80
. Raman test was carriers left. Fortunately, the inner carbon layer core in the TiO2/C
run on a LabRAM HR Evolution system with Ar ion laser (514.5 nm). hollow sphere can absorb large amount of the generated electrons
XPS was recorded on the ESCA300 XPS machine. The UVeVis and stop the electronehole pairs from recombination, as a result
absorbance spectra were acquired on the UV-2550 (Shimazu, large numbers of active holes left in the VB which will improve the
Japan). photocatalytic activity of the photocatalyst.
The photocatalytic activity was evaluated by photo-degradation Fig. 1 shows the FESEM images of the hydrothermal product and
of Rhodamine B (RhB) in an aqueous solution. 50 mg of the as- the TiO2/C composites with different TBOT amount added. Fig. 1a
prepared samples were dispersed in 80 mL RhB aqueous with the shows the SEM of hydrothermal product which performs the
concentration of 20 mg L1. Before the irradiation, the photo-
catalyst was immersed into the equal content MB solution for more
than 4 h to reach saturation adsorption in dark. A 500 W mercury
lamp was used as the UV light source. The change in the RhB
concentration with time was monitored by UVeVis spectropho-
tometry (UV-2550, Shimazu, Japan). The self-degradation data was
investigated without any samples instead of the as-prepared
photocatalyst.

3. Results and discussion

Scheme 1 illustrates the schematic diagram of the preparation

process of TiO2/C hollow sphere. After hydrothermal reaction from
glucose and SDS mixed solution, the hollow carbon sphere can be
produced. The SDS plays an important role in this process of
forming hollow sphere and we found the hollow structure cannot
be formed without SDS. TiO2 was coated on the outer surface of
carbon hollow sphere by the traditional solution method from the
precursor of TBOT in alcohol. Here, the content of TiO2 can be
adjusted by the consumption of TBOT precursor. Less TiO2 coated
will lead to low photocatalytic activity because of shortage of
photocatalyst. But much more TiO2 coated lead to a thicker layer of
photocatalyst which will block the photo-generated electrons
transferred to the inner carbon layer core and as a result little Fig. 1. SEM images of carbon hollow sphere (a), TiO2/C-0.2 (b), TiO2/C-1 (c), and TiO2/
enhancement of photocatalytic activity would be performed. When C-5 (d). The inset in (a) is the TEM image for carbon hollow sphere, the scale bar is
the as-prepared TiO2/C hollow sphere employed as photocatalyst, 500 nm.
86 Y. Zhuang et al. / Journal of Alloys and Compounds 662 (2016) 84e88

uniform spherical microstructure with the diameter of ~200 nm.

And the inset TEM image (Fig. 1a) proves that the carbon sphere is
hollow inside. After coating TiO2 in TBOT, the morphologies of TiO2/
C-0.2 (Fig. 1b) and TiO2/C-1 (Fig. 1c) still keep spherical except the
diameters enlarged in different degrees. While the TiO2/C-5
(Fig. 1d) spheres are aggregated and enlarged further. From the SEM
and TEM images, it can be concluded that a coreeshell hollow
sphere structure with a shell coating on the carbon hollow spheres
core may have been prepared and the thickness of coating layer
depends on the amount of TBOT added.
To further prove the hollow structure and understand the
composition of the final product, TEM and HRTEM images were
investigated, as shown in Fig. 2. Fig. 2 shows the TEM images of
TiO2/C-1 which illustrate that the microstructure of the product is
hollow sphere (Fig. 2a) and the sphere consist of two layers
(Fig. 2b). The inner layer is amorphous which can be attributed to
the amorphous inner carbon core layer. The outer layer is crystal
and the distinct lattice fringe at 0.32 nm can be assigned to the d-
spacing of (110) planes of rutile TiO2 (JCPDS 12-1276) which is also
agree well with the result of XRD data. The phase and crystal
structure of the products have been investigated by XRD, as shown
in Fig. 3a. The products with different TBOT amount perform the
very similar diffraction patterns, which attribute to mixed phase of
large amount of rutile (JCPDS 12-1276) with little anatase (JCPDS
21-1272) of TiO2. The Raman spectra in Fig. 3b also present the
same result. Only two peaks located at 1365 and 1605 cm1 are
observed in the spectra of pure carbon sphere which are attributed
to G and D bands of amorphous carbon [5]. Several peaks (located at
143, 397, 520 and 637 cm1 respectively) are found in the spectra of
pure TiO2, which are assigned to the vibration mode of TiO2 [5]. The
peaks observed in the final product (TiO2/C-1) composed of all the
peaks found in the spectra of pure carbon sphere and pure TiO2,
which means that the final product is the composite of TiO2 and
amorphous carbon. XPS is adopted to further investigate the
chemical composition of the amorphous, as shown in Fig. 4a. Two
peaks can be found in the high resolution C1s XPS result, in which
the strong peak located at 284.2 eV corresponds to CeC bond while
a weak peak at 285.7 eV corresponds to CeO species, indicating the
carbon is not carbonized completely [22,23]. The XRD, Raman and Fig. 3. (a) XRD for TiO2/C-0.2 (1), TiO2/C-1 (2), and TiO2/C-5 (3). (b) Raman spectra for
pure carbon sphere, pure TiO2 and TiO2/C.
XPS results further suggest that the product (TiO2/C-1) consists of
TiO2 and amorphous carbon. Thus, it can be concluded that the
TiO2/C coreeshell hollow sphere has been prepared successfully 600
C in air shows a clear absorption edge at around 400 nm
which will be an excellent photocatalyst for photo-degradation of corresponding to band-gap absorption of intrinsic TiO2. While the
organic compounds in contaminative water, due to the large sur- TiO2/C coreeshell composites perform red shift and higher absor-
face area exposing and high photocatalytic activity of TiO2 and in- bance by different degrees because of the inner carbon layer
ner carbon layer which can serve as acceptor for photo-generated serving as the acceptor of photo-generated electrons and increasing
electrons and stop the photo-generated electronehole pairs from the absorbance of light. Furthermore, the higher the TiO2 content in
recombination. the composites, the lower the absorbance because of the relative
To investigate the absorbance property of the as-prepared lower content of carbon and thicker TiO2 layer around the carbon.
samples, the UVeVis spectrum was employed in this study, as The UVevis spectra suggest that the TiO2/C coreeshell hollow
shown in Fig. 4b. The pure TiO2 obtained from annealing TiO2/C-1 at sphere will perform higher photocatalytic activity than that of pure
TiO2 hollow sphere, considering the higher light absorbance and
red shift of the absorption edge of TiO2/C coreeshell hollow sphere.
The photocatalytic activity of the as-prepared photocatalysts
was evaluated by degrading RhB (20 mg L1) under UV light irra-
diation at room temperature. Fig. 5a shows the concentration of
RhB changing with the irradiation time of the as-prepared TiO2/C
composite photocatalysts synthesized at different TBOT contents
and pure TiO2 hollow sphere compared to self-degradation. The
TiO2/C-1 coreeshell hollow sphere performs the highest photo-
catalytic activity that the RhB can be degraded by more than 90%
within 2 h irradiation referenced to the less than 10% of self-
degradation, due to the photo-generated electrons acceptor of
carbon layer in the coreeshell structure that stopping the recom-
Fig. 2. TEM (a) and HRTEM (b) of TiO2/C hollow sphere. bination of photo-generated electronehole pairs, thus improving
 Y. Zhuang et al. / Journal of Alloys and Compounds 662 (2016) 84e88
Fig. 4. (a) High resolution XPS of C1s. (b) UVeVis absorbance spectra for TiO2/C-0.2 (d),
TiO2/C-1 (c), and TiO2/C-5 (b) compared to pure TiO2 (a).
the photocatalytic activity obviously. The TiO2/C-0.2 shows very
weak activity because of the low content of the photo sensitive TiO2
in the TiO2/C-0.2 composite. Although the TiO2/C-5 presents much
higher activity than that of TiO2/C-0.2, it is much lower than that of
TiO2/C-1, resulting from the large thickness of TiO2 outside the
carbon layer as a result the photo-generated electrons cannot
transfer to the carbon layer freely and speedily. Therefore, the
carbon layer in TiO2/C-5 photocatalyst makes small contribution to
the whole photocatalytic activity and just the similar level with
pure TiO2 hollow sphere. The photo-degradation behavior of RhB in
the presence of the photocatalyst obeys the first-order reaction
kinetics expressed as ln(C0/C) ¼ kt, where k (h1) is the rate con-
stant, t (h) is the irradiation time, and C0 and C are the initial and
RhB concentrations in the aqueous solution, respectively. As shown
in Fig. 5b, the k values of TiO2/C-0.2, TiO2/C-1, TiO2/C-5, and pure
TiO2 are calculated to be 0.152, 1.262, 0.789, and 0.675 h1
respectively, while the self-degradation is only 0.042 h1, as listed
in Fig. 5b. The k value of highest photocatalytic activity of TiO2/C-1
composite sphere reaches 1.262 h1 which is almost twice as high
as the pure TiO2 of 0.675 h1. Therefore, the TiO2/C-1 coreeshell
hollow sphere owns a suitable thickness of TiO2 around the outside
of inner carbon layer, and the photo-generated electrons can
transfer to the carbon layer from photo sensitive TiO2 layer freely
and speedily, thus promote the photocatalytic activity.
87
Fig. 5. (a) Concentration (C) changes of RhB in the aqueous solution as a function of UV
illuminating time in the presence of the photocatalyst of TiO2/C-0.2 (1#), TiO2/C-1 (2#),
and TiO2/C-5 (3#), TiO2 (4#) compared to self-degradation (5#). The photo-
degradation reaction follows the first-order reaction kinetics and the apparent rate
constants (k) are listed in (b).
4. Conclusion
TiO2/C coreeshell hollow sphere has been prepared by a tradi-
tional hydrothermal reaction and followed by solution method and
annealing under Ar atmosphere. The as-prepared TiO2/C coreeshell
hollow sphere performs a slight red shift and higher absorbance
than that of pure TiO2 hollow sphere, resulting in higher photo-
catalytic activity under UV irradiation. The TiO2/C coreeshell hol-
low sphere photocatalyst owns excellent photocatalytic activity
that the RhB can be photo-degraded by more than 90% under two
hours' UV irradiation comparing to 70% of pure TiO2 hollow sphere
photocatalyst. By comparing the rate of reaction kinetics, the rate of
TiO2/C coreeshell hollow sphere is twice as high as the pure TiO2.
The results suggest that the as-prepared TiO2/C coreeshell hollow
sphere is a promising candidate in waste water treatment
application.
Acknowledgments
The authors gratefully thank the financial supports from the
National Natural Science Foundation of China (Contract Number:
21373103) and Jiangsu Province Natural Science Foundation (No.
BK2011260).
88 Y. Zhuang et al. / Journal of Alloys and Compounds 662 (2016) 84e88

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