Applied Surface Science 268 (2013) 237–245

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Applied Surface Science

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Fabrication and photocatalytic properties of spheres-in-spheres ZnO/ZnAl2 O4

composite hollow microspheres
Li Zhang a,b , Jianhui Yan a,b , Minjie Zhou b , Yahui Yang a , You-Nian Liu a,∗
a
College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, PR China
b
School of Chemistry and Chemical Engineering, Hunan Institute of Science and Technology, Yueyang, Hunan 414006, PR China

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

Article history: ZnO/ZnAl2 O4 composite hollow microspheres have been fabricated using glucose as template by
Received 22 July 2012 a polyethylene glycol (PEG-4000)-assisted one-pot hydrothermal method. The as-prepared samples
Received in revised form 8 December 2012 were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), UV–vis diffusive
Accepted 12 December 2012
reflectance spectroscopy (DRS), Brunauer–Emmett–Teller (BET) measurement and X-ray photoelectron
Available online 3 January 2013
spectroscopy (XPS). The effects of the content of ZnO(X) and the molar ratio of glucose to metal ion (R) on
the structure, composition, morphology and textural properties of the as-prepared samples were inves-
Keywords:
tigated in detail. The results indicated that a novel spheres-in-spheres ZnO/ZnAl2 O4 composite hollow
ZnO/ZnAl2 O4
Spheres-in-spheres
microspheres (designated as S@S-ZnO/ZnAl2 O4 ) could be obtained as X = 25 mol% and R = 1. In addition,
Composite hollow microsphere the photocatalytic activity of the as-prepared samples was evaluated by photocatalytic decolorization of
Photocatalytic activity methyl orange (MO) aqueous solution under the irradiation of the simulated sunlight (100 mW/cm2 ). The
maximum photocatalytic decoloration rate of 98.7% within 60 min was obtained at 0.5 g L−1 concentra-
tion of S@S-ZnO/ZnAl2 O4 photocatalyst, which exceeded that of Degussa P25 under the same conditions.

© 2012 Elsevier B.V. All rights reserved.

1. Introduction nanoparticles exhibited an average size of approximately 5 nm

Since Fujishima and Honda reported the evolution of oxygen
and hydrogen from a TiO2 electrode under the irradiation of light in
1972 [1], many different semiconductors, such as ZnO, Fe2 O3 and
CdO. have been used as photocatalysts for the photodegradation
of organic or inorganic pollutants in hazardous waste [2–4]. With
a broad bandgap of 3.8 eV, spinel ZnAl2 O4 has been attracting
considerable attention since it can be used as catalyst [5], catalyst
support [6], and even as optical material [7] due to its high thermal
stability, low surface acidity, and high mechanical resistance[8].
However, one of the problems arising from the application of
ZnAl2 O4 in the catalysis field is its low surface area. Previous stud-
ies indicated that the photocatalytic activity of catalysts depended
strongly on adsorption behavior and the separation efficiency of e−
and h+ pairs. The adsorption capacity can be generally improved
by increasing the specific surface area of catalysts. Toward this
end, Visinescua et al. [9] synthesized ZnAl2 O4 using starch as
fuel at low-temperature and obtained the high surface area pow-
ders. Conrad et al. [10] prepared nanostructure Cux Zn1−x Al2 O4
by a microwave-assisted hydrothermal synthesis. The spinel
∗ Corresponding author. Tel.: +86 731 8883 6964; fax: +86 731 8887 9616.
E-mail address: liuyounian@csu.edu.cn (Y.-N. Liu).
and a high specific surface area (above 250 m2 g−1 ). The separation
efficiency of e− and h+ pairs can be achieved by building junctions
and chemical potential gradients into the catalyst, such as coating
of noble metal nanoparticles [11–13], doping of nonmetal ions
[14–16], and composite of different semiconductors [17,18].
ZnO with a direct band gap of 3.2 eV and an indirect band gap of
2.45 eV has been recognized as the excellent materials for photo-
catalytic process due to their high photosensitivity, nontoxic nature
[19–22]. It is even more efficient than TiO2 in the photodegrada-
tion [23]. However, the quick recombination of e− and h+ pairs is the
major limitation in achieving high photocatalytic efficiency. Studies
indicated that the composite between ZnO and another nonsensi-
tive semiconductor (usually have very wide bandgap), e.g., In2 O3
(Eg 3.6 eV) [24], SnO2 (Eg 3.8 eV) [25], and NiO (Eg 3.5 eV) [26] also
has been proved to be an effective method to improve their pho-
tocatalytic activity. In particularly, the coupling of the bandgap
structure of both ZnO and ZnAl2 O4 phase in the ZnO/ZnAl2 O4
nanocomposite ensured the efficient separation of photogenerated
e− and h+ pairs, which was prerequisite for the enhanced pho-
tocatalytic performance [27]. However, conventional powdered
photocatalysts have a serious limitation to post-treatment sepa-
ration in a slurry system after photocatalytic reaction. If powered
photocatalysts can be fabricated into hollow spheres, which can
be more readily separated from the slurry system by filtration or

0169-4332/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2012.12.069
238 L. Zhang et al. / Applied Surface Science 268 (2013) 237–245

sedimentation after photocatalytic reaction than conventional samples were obtained using a UV–vis spectrophotometer (UV-
powder photocatalysts [28]. 2550, Shimadzu, Japan). BaSO4 was used as a reflectance standard in
Herein, a novel spheres-in-spheres ZnO/ZnAl2 O4 composite hol- a UV–vis diffuse reflectance experiment. Brunauer–Emmett–Teller
low microspheres (S@S-ZnO/ZnAl2 O4 ) were fabricated by one-pot (BET) surface areas (SBET) were determined by the nitrogen absorp-
hydrothermal method. The structure, composition, morphology, tion isotherms apparatus (ST-08 analyzer). All the samples were
textural, UV–vis absorbing properties and elemental composi- degassed at 200 ◦ C overnight before the measurements. The chemi-
tion of the resulting composites were investigated by SEM, XRD, cal composition was analyzed by X-ray photoelectron spectroscopy
BET, nitrogen adsorption, UV–vis spectra and XPS techniques. (XPS with Mg-K␣ radiation).
Subsequently, the photocatalytic activities of the ZnO/ZnAl2 O4
composites were evaluated by the decolorization of MO and a pos- 2.3. Measurement of photocatalytic activity
sible formation mechanism of S@S-ZnO/ZnAl2 O4 was discussed.
The decolorization of MO (used as a contamination model) was The photocatalytic reaction was carried out in homemade tube-
tested in order to demonstrate the potential environmental appli- shaped quartz reactor including three layers connected with gas
cation of S@S-ZnO/ZnAl2 O4 for the removal of contaminants from collecting devices, and water was used as the external circulation
wastewater. cooling and wind as the internal cooling. The reaction temperature
was kept at 25 ± 0.2 ◦ C by controlling the external circulation water
in the water jacket of the reactor during the entire experiment.
2. Experimental
The photocatalyst powder (0.3 g) was dispersed by a magnetic stir-
rer in a 600 ml MO solution with the concentration of 25 mg L−1 .
2.1. Sample preparation
A 150-W xenon lamp with  = 200–900 nm was used as the sim-
ulated sunlight source. The luminous intensity was measured at
All chemicals were analytical grade and were used without
100 mW/m2 by the auto-range ST-85 optical radiometer (Photo-
further purification. Pure ZnAl2 O4 sample was prepared by a poly-
electric Instrument Factory of Beijing Normal University). Prior
ethylene glycol (PEG)-assisted hydrothermal synthetic method
to light illumination, the suspension was strongly magnetically
using the glucose based carbonaceous materials as template. In
stirred for 30 min in the dark for adsorption/desorption equilib-
a typical synthetic procedure, a mixture of Zn(NO3 )2 ·6H2 O and
rium. During irradiation, the catalyst was kept in suspension state
Al(NO3 )3 ·9H2 O with Al/Zn molar ratio of 2.0 according to the stoi-
by a magnetic stirrer. Samples for analysis were extracted through
chiometric ratio were dissolved in deionized water to obtain a
pipette every 10 min and centrifuged immediately. Absorbance
solution with a total cationic concentration of 0.3 M, and polyeth-
of the suspension and initial solution was determined, respec-
ylene glycol (PEG, as a dispersion agent, ensuring that the content
tively. A 752 UV–vis spectrophotometer was used at the maximum
of PEG in catalysts was 10 wt.%) was subsequently added with con-
absorption wavelength (max = 465 nm) of MO. Decoloration rate
stant stirring to the above solution until complete dissolution. Then
are presented as C/C0 , where C0 and C are the initial concentra-
ammonia solution (NH3 ·H2 O) was added dropwise into the mixture
tion of MO under adsorption equilibrium and the concentration
solution under magnetic stirring until the pH reached 9.0 (solution
of MO at different irradiation time, respectively. Experiments for
A); A certain amount of glucose (as a template agent) were dis-
comparison were carried out under the same condition, but one
solved in distilled water to form a glucose solution (solution B).
was done without catalyst and another was in the dark. Each set
Solutions A and B were mixed to ensure the molar ratio of glu-
of photocatalytic measurements was repeated three times, and the
cose to metal ion (R) varied from 0 to 2. After mixing, the reaction
experimental error was found to be within ±5%.
solution was transferred into a 200 ml Teflon-lined autoclave. The
At the same time, the concentration of MO in the filtrate was
autoclave was sealed and kept at 180 ◦ C for 24 h, and then cooled to
measured by COD method. The COD/COD0 were calculated based
room temperature naturally. After filtration and washing with dis-
on the concentration difference of MO before and after irradiation.
tilled water and ethanol for several times, the obtained sample was
dried in oven at 80 ◦ C overnight. Finally, the samples were obtained
3. Results and discussion
after annealing under certain temperatures.
ZnO/ZnAl2 O4 composite was prepared through a procedure sim-
3.1. SEM images
ilar to that mentioned above except that Al/Zn molar ratio was
smaller than stoichiometric according to the literature [29]. The
The morphology of ZnAl2 O4 and ZnO(x mol%)/ZnAl2 O4 samples
final sample was denoted as ZnO(x mol%)/ZnAl2 O4 , where x mol%
prepared with a certain ratio of glucose to metal ion (R = 1) at 500◦ C
represents molar percent difference of Al(NO3 )3 ·9H2 O (the stoi-
for 4 h was investigated by SEM in Fig. 1. Fig. 1a–d show that all the
chiometric minus the added amount), namely the formed molar
samples are nearly in spherical shape with diameters of ca.1–3 ␮m
percent of ZnO.
in the present of glucose, and especially some microspheres are
In our experiments, five different annealing temperatures were
open and hollow due to the removal of carbon by calcination.
adopted: 500, 600, 700, 800 and 900 ◦ C, respectively. Samples with
This indicates that glucose plays a critical role for the formation of
different Al/Zn ratios (varying from 1.3 to 1.7) in the starting mate-
the hollow microspheres. However, with increasing x, the micro-
rials are prepared under identical conditions, in order to investigate
spheres particles size and surfaces change, some of which are not
the role of composition on the photocatalytic activities. For com-
flat with rough superstructure.
parison, pure ZnO and ZnAl2 O4 nanoparticles are also prepared.
3.2. XRD study
2.2. Characterization
Fig. 2 shows XRD patterns of ZnAl2 O4 , ZnO(x mol%)/ZnAl2 O4
The crystalline phase and the crystal size of the samples were and ZnO samples prepared with a certain ratio of glucose to metal
identified by X-ray diffraction (XRD, Bruker D8) using Cu K␣ radia- ion (R = 1) at 500◦ C for 4 h. It is obvious that five main diffraction
tion (= 1.5418 Å) at a scan speed of 0.05◦ s−1 , a voltage of 40 kV and a peaks of the (2 2 0), (3 1 1), (4 2 2), (5 1 1) and (4 4 0) reflections are
current of 300 mA. The surface morphologies of the samples were observed in Fig. 2a, which can be indexed to spinel ZnAl2 O4 (JCPDS
observed by scanning electron microscope (SEM, Nova Nano230) Card No. 05-0669). This result is in agreement with the reported
operated at 30 kV. UV–vis diffused reflectance spectra of the data [30]. The fact that no peak characteristic of any other phase
 L. Zhang et al. / Applied Surface Science 268 (2013) 237–245 239

Fig. 1. SEM images of the prepared ZnAl2 O4 and ZnO (x mol%)/ZnAl2 O4 samples. (a) ZnAl2 O4 ; (b) ZnO(15 mol%)–ZnAl2 O4 ; (c) ZnO(25 mol%)–ZnAl2 O4 ; (d)
ZnO(35 mol%)–ZnAl2 O4. .

or impurity is observed in the XRD pattern implies high purity of
ZnAl2 O4 crystalline phase synthesized in this work. Fig. 2b–d shows
that all the patterns of ZnO (x mol%)/ZnAl2 O4 are very similar. The
intensity of ZnO peaks is lower than that of ZnAl2 O4 in the pat-
terns of ZnO (x mol%)/ZnAl2 O4 . This result can be attributed to the
fact that main diffraction peaks of ZnO are very close to those of
ZnAl2 O4 and covered by the diffraction peaks of ZnAl2 O4. In addi-
tion, the amount of ZnO is relatively lower than that of ZnAl2 O4 . The
crystalline sizes of ZnO(x mol%)/ZnAl2 O4 are estimated from XRD
reflections by the Scherrer equation [31]. The particle sizes of ZnO(x
mol%)/ZnAl2 O4 are 9.3, 9.1 and 8.3 nm for x = 15, 25 and 35, respec-
tively. Fig. 2e shows the typical XRD pattern of the as-prepared
ZnO. All diffraction peaks can be indexed to wurtzite structure of
ZnO, which is in good agreement with the literature values (JCPDS
card, No. 36-1451). The sharp diffraction peaks indicate the good
crystallinity of the synthesized ZnO. No peaks of other impurities
are appeared in the patterns, suggesting that only single-phase ZnO
samples were formed.
The content of ZnO has an obvious influence on the physical
properties of the ZnO(x mol%)/ZnAl2 O4 samples. The pore volume
of as-prepared ZnO(x mol%)/ZnAl2 O4 samples increases gradually
in inversely with average pore size with increasing x up to 25, at
this point the pore volume reaches the maximum and the average
pore size reaches the minimum. This indicates that the pore volume
decreases with increasing average pore size, which is consistent
with previous reports [32]. With increasing x, the BET surface
area increases and reaches its highest value of 158.27 m2 g−1 at
x = 25. However, when x is further increased to 35, the surface
area of the ZnO(x mol%)/ZnAl2 O4 sample decreases from 158.27 to
96.99 m2 g−1 . Consequently, specific surface area of the obtained
ZnO(x mol%)/ZnAl2 O4 has proved to be strongly dependent on
the composition. Such phenomena are closely related with the
structural feature of different ZnO/ZnAl2 O4 composites. Moreover,
Table 1
Effects of the content of ZnO on the textural properties of ZnO (x mol%)/ZnAl2 O4
samples.

3.3. BET surface area ZnO/ZnAl2 O4 molar BET surface Pore size Pore volume
ratio area (m2 g−1 ) (nm) (cm3 g−1 )

Table 1 shows the BET surface area, pore volume, and aver- 15% 129.85 8.85 0.29
age pore size of ZnO(x mol%)/ZnAl2 O4 samples prepared with 25% 158.27 8.82 0.35
35% 96.99 9.24 0.22
a certain ratio of glucose to metal ion (R = 1) at 500◦ C for 4 h.
240 L. Zhang et al. / Applied Surface Science 268 (2013) 237–245

Fig. 2. The XRD patterns of the prepared ZnAl2 O4 , ZnO (x mol%)/ZnAl2 O4 and ZnO
samples. (a) ZnAl2 O4 ; (b) ZnO(15 mol%)–ZnAl2 O4 ; (c) ZnO(25 mol%)–ZnAl2 O4 ; (d)
ZnO(35 mol%)–ZnAl2 O4 ; (e) ZnO. .

the porous structure is believed to facilitate the transportation of

reactant molecules and products through the interior space due to
the interconnected porous networks and to favor the harvesting of
exciting light due to enlarged surface area and multiple scattering
within the porous framework [33,34]. We further investigated the
effects of the content of ZnO on the pore structure based on nitrogen
adsorption and desorption measurements.

3.4. Nitrogen adsorption studies

Fig. 3 shows the N2 adsorption–desorption isotherm and

the corresponding pore-size distribution curve for the ZnO(x
mol%)/ZnAl2 O4 samples prepared with a certain ratio of glu-
cose to metal ion (R = 1) at 500◦ C for 4 h. Fig. 3a shows
that all the samples have a type IV isotherm according to
Brunauer–Deming–Deming–Teller (BDDT) classification with two
capillary condensation steps, implying bimodal pore size distri-
butions in the mesoporous (2–50 nm) and macroporous (>50 nm)
regions [35]. With increasing x, the shapes of nitrogen adsorption
and desorption isotherms underwent obvious changes, implying
a significant variation of pore structures. Firstly, the isotherms
corresponding to the samples obtained at x = 15 and 25 (com-
pared with that at x = 35) show higher absorption at high relative
pressures (P/P0 approaching 1), indicating the formation of larger
inter-aggregated pore between the secondary aggregated particles
[32,36] and/or an increasing pore volume of interaggregated pores,
as further confirmed in Fig. 3b. This may be related to the hollow-
ing of the interior space of ZnO/ZnAl2 O4 microspheres (as shown in
Fig. 1b and 1c). For the sample obtained at x = 25, the bimodal pore-
size distribution consisting of fine intra-aggregated pores with a
maximum pore diameters of 6.2 nm and larger inter-aggregated
pores with a maximum pore diameter of 46.4 nm. These meso-
pores and macropores presumably arise from the interstices among
the different-sized nanoparticles within the shells of ZnO/ZnAl2 O4
hollow microspheres. When x was further increased to 35, the
hysteresis loop shifted to relative lower pressure (P/P0 ) region
(0.4 < P/P0 < 0.9), implying the formation of finer intra-aggregated
pore within the primary agglomerated particles [37], as con-
firmed by a drastic decrease in the corresponding pore volume
(Fig. 3b). The maximum pore diameter of larger interaggregated
pores increases to 216.4 nm. This may due to the collapse of inter-
aggregated mesopores in addition to smaller BET surface areas
Fig. 3. Nitrogen adsorption–desorption isotherms (a) and pore size distribution
curves (b) of ZnO(x mol%)/ZnAl2 O4 samples.
(a) ZnO(15 mol%)–ZnAl2 O4 ; (b) ZnO(25 mol%)–ZnAl2 O4 ; (c) ZnO(35 mol%)–ZnAl2 O4 .
(see Table 1). Higher specific surface area benefits the adsorption
of reagent on the surface of photocatalysts and enhancement of
photocatalytic efficiency. Subsequent characterizations have been
focused on the selected ZnO(25 mol%)/ZnAl2 O4 hollow spherical
structures.
3.5. SEM images
ZnO(25 mol%)/ZnAl2 O4 hollow microspheres prepared with
different ratio of glucose to metal ion (R) at 500◦ C for 4 h were
investigated by SEM in Fig. 4. In the absence of glucose, the
products are solid particles with no hollow microsphere structure
(Fig. 4a). The hollow structures are readily formed as glucose added
into the reaction system. At R = 0.5, hollow microspheres can be
observed, but no regularly morphology can be obtained due to the
lower glucose ratio yields a more robust and thicker shell (Fig. 4b).
As shown in Fig. 4c, R increases to a certain degree (R = 1), most
of the microspheres appear to have hollow interiors. To get more
information about the hollow structures, SEM images (Fig. 4d)
further confirms the presence of hollow structures and the rough
external shells of the hollow microspheres consisted of loosely
packed nanoparticles. Especially a quite unique structures with a
distinguishable smaller sphere inside the rough external shell can
be clearly observed by the broken hollow microspheres, a socalled
“spheres-in-spheres” (S@S) structure. However, when R increases
 L. Zhang et al. / Applied Surface Science 268 (2013) 237–245 241

Fig. 4. SEM images of ZnO(25 mol%)/ZnAl2 O4 samples prepared with varying R. (a) R = 0; (b) R = 0.5; (c) R = 1; (d) R = 1 Magnified image of the broken hollow spheres indicating
S@S structure; (e) R = 2.

further to 2, the external shells of the hollow microspheres are pro- collapsed during calcination [38]. Therefore, it can be deduced
gressively thinned and the hollow microspheres become broken that the ratio of glucose to metal ion in the reactants play a key
(Fig. 4e), which can be attributed to the fact that a great deal of car- role in controlling the hollow architecture, and shell thickness
bon dioxide was produced and caused hollow microspheres easily of microspheres. The higher glucose ratio lead to a thinner shell,
242 L. Zhang et al. / Applied Surface Science 268 (2013) 237–245

Fig. 5. UV–vis diffuse reflectance spectra of the S@S-ZnO/ZnAl2 O4 (a) and ZnAl2 O4
samples (b).

whereas the lower glucose ratio yields a more robust and thicker
shell. Thus, the shell thickness of the hollow microspheres can be
easily tailored by varying the ratio of glucose to metal ion in the
solution, which is in good agreement with the previous report
[39].

3.6. UV–vis diffuse reflectance spectra

The UV–vis diffuse reflectance spectra (Fig. 5a) of as-obtained

S@S-ZnO/ZnAl2 O4 displays a significant increase in the absorption
at wavelength ≤ 400 nm compared with pure ZnAl2 O4 (Fig. 5b). Fur-
thermore, it can be seen that S@S-ZnO/ZnAl2 O4 sample shows a
certain absorption in the visible light region (the wavelength ran-
ging from 400 to 800 nm), while no absorption can be observed
for pure ZnAl2 O4. This experimental result can be attributed to
the coupling interaction between the ZnO and ZnAl2 O4 phase, the Fig. 6. XPS survey spectrum of the S@S-ZnO/ZnAl2 O4 sample. (a) Full XPS spectra;
(b) Zn2 p spectra.
optimizing content of ZnO and the form of heterojunction struc-
ture, which leads to the enhancement of utilization of light and
photocatalytic activity [27,40]. Additionally, the absorption of S@S- 3.8. Formation mechanism of the S@S-ZnO/ZnAl2 O4 structures
ZnO/ZnAl2 O4 sample in the visible light region may be due to the
doping of carbon resulted from glucose template, which was not The pure ZnAl2 O4 phase formed according to the following reac-
totally removed during calcination. tion steps:

Zn2+ + 2Al3+ + 8OH− (pH9) → Zn(OH)2 ↓ + 2Al(OH)3 ↓

3.7. XPS studies → ZnAl2 O4 ·4H2 O → ZnAl2 O4 + 4H2 O.

The elemental composition of the S@S-ZnO/ZnAl2 O4 sample was
further determined by X-ray photoelectron spectroscopy (XPS). The
XPS survey spectrum (Fig. 6a) indicates that the prepared S@S-
ZnO/ZnAl2 O4 sample consists of Zn, O, Al and C elements. The C
element may mainly be ascribed to the adventitious hydrocarbon
from XPS instrument itself. While the atomic ratio of Zn:Al:O is
estimated to be 1:1.5:3, which is not in good agreement with the
nominal atomic composition of ZnAl2 O4 , indicating the presence of
other phase besides ZnAl2 O4 . The peaks (Fig. 6b) observed at 1021.9
and 1045 eV can be ascribed to Zn2 p3/2 and Zn2 p1/2 of the metallic
zinc, respectively. The XPS spectrum of O1 s (data not shown) dis-
plays that the main peak located at 531 eV. According to previous
reported in the literatures [28], the Zn2 p3/2 peak at 1021.9 eV and
the O1 s peak at 531 eV can be assigned to Zn and O elements in
ZnO, respectively. Thus, both XRD and XPS analysis indicate that
the as-prepared hollow microspheres are composed of ZnO and
ZnAl2 O4.
When the ratio of Al to Zn was smaller than stoichiometric
ratio, the ZnO/ZnAl2 O4 composite formed between excess ZnO
and ZnAl2 O4 by calcination. At the hydrothermal conditions, glu-
cose is easy to be dehydrated and form the carbon microspheres.
The mechanism of the formation of the single hollow spheres
using carbon-precursor based templates has been investigated
[41], which generally involves the formation of the carbon micro-
spheres as the cores by polymerization and carbonization reaction
in the initial reaction step and subsequently the dehydration of
hydrolyzed metal hydrates to form the shells on the hydrophilic
carbon cores. In our experiment, the unique S@S-ZnO/ZnAl2 O4
structure implies that its reaction mechanism could be differ-
ent from the previously reported mechanisms for single hollow
spheres. The formation of S@S-ZnO/ZnAl2 O4 probably involves five
steps. The dehydration, polymerization and carbonization of glu-
cose under hydrothermal conditions can lead to the formation
of primary carbonaceous spheres [42] (step I). The surface of the
 L. Zhang et al. / Applied Surface Science 268 (2013) 237–245
Fig. 7. Effect of the content of ZnO on the photocatalytic activity of the
ZnO(x mol%)/ZnAl2 O4 samples. (a) ZnAl2 O4 ; (b) ZnO(15 mol%)–ZnAl2 O4 ; (c)
ZnO(25 mol%)–ZnAl2 O4 ; (d) ZnO(35 mol%)–ZnAl2 O4 ; (e) ZnO; (f) Light irradiation;
(g) ZnO (25 mol%)–ZnAl2 O4 in dark.
spheres is hydrophilic and contains a large amount of OH and
C O groups due to non-or just partially dehydrated glucose [43].
Importantly, the hydrophilic groups on the surfaces of the newly
formed carbonaceous primary spheres may act as the “nuclei sites”
for gradually binding metal cations through coordination or elec-
trostatic interactions and lead to the formation of the carbonaceous
sphere as cores and a shell of Zn(OH)2 and Al(OH)3 on the outside
wall of the carbon spheres (step II). The thus-formed Zn(OH)2 and
Al(OH)3 shell on the surface of the carbonaceous spheres may fur-
ther react with the -OH groups formed via the dehydration and
polymerization of the other residual glucose, which forms the sec-
ondary carbon shell outside the Zn(OH)2 and Al(OH)3 layers (step
III). Further hydrolysis of metal salt will provide additional metal
source to form the outer shell (step IV) upon further condensation of
Zn(OH)2 and Al(OH)3 species and eventually leading to the forma-
tion of Zn–carbon composites in hydrothermal treatment process.
Finally, the removal of carbon cores, and densification and cross-
link of incorporating metal cationic ions in the layer via calcination
results in the formation of S@S-ZnO/ZnAl2 O4 (step V).
Our experiments also show that the molar ratio of glucose to
metal ion is a key factor for the formation of S@S-ZnO/ZnAl2 O4
structure. When the ratio of glucose to metal ion is relatively low
(0.5), the dehydration, polymerization and carbonization process of
glucose might be comparable with the hydrolysis process of metal
salt, thus the formation of Zn–carbon composites can be in a rela-
tively random manner, leading to the formation of irregular hollow
structure (Fig. 4b). Whereas the ratio of glucose to metal ion was
increased to 1, the dehydration, polymerization and carbonization
process could become predominant in the initial step (step I) of
the reaction and lead to the formation of the carbonaceous sphere
as cores. However, with increasing amount of glucose to 2, lesser
metal ions incorporated leads to the formation of thinner shells,
which caused ZnO/ZnAl2 O4 microspheres break up and no reg-
ularly morphology can be obtained (Fig. 4e). Therefore, it is not
surprising that the thickness of shell can be easily controlled by
changing R. Further detailed studies are in progress to understand
the mechanism.
3.9. Photocatalytic activity
Fig. 7 displays the effect of composition of ZnO(x mol%)/ZnAl2 O4
samples prepared at R = 1 on the decolorization of MO. For com-
parison, under dark conditions without light irradiation, the
243
concentration of MO almost does not change for every mea-
surement in the presence of ZnO(25 mol%)/ZnAl2 O4 sample. Light
irradiation in the absence of any samples almost does not result in
the photocatalytic decolorization of MO, indicating that the pho-
tolysis of MO can be ignored. Therefore, the presence of both light
irradiation and ZnO(x mol%)/ZnAl2 O4 photocatalysts are neces-
sary for the efficient degradation. However, compared with pure
ZnAl2 O4 and ZnO, all the ZnO (x mol%)/ZnAl2 O4 composites have a
higher photocatalytic activity under simulated sunlight irradiation.
For ZnO, the CB bottom and the VB top lie at −4.19 and −7.39 eV,
with respect to absolute vacuum scale (AVS). While for ZnAl2 O4 ,
the CB bottom and VB top lie at −3.36 and −7.16 eV vs. AVS [27].
Both the CB bottom and the VB top of ZnO lay below the CB bot-
tom and VB top of ZnAl2 O4 , respectively. When they are coupled
together, photons may be absorbed in both ZnO and ZnAl2 O4 and
form the e− and h+ pairs. The electrons at the CB bottom of ZnAl2 O4
would migrate to that of the ZnO; whereas holes at the VB top of
ZnAl2 O4 would remain there. On the other hand, the holes at the
VB top of the ZnO would migrate to that of ZnAl2 O4 , with electrons
at the CB bottom of ZnO remaining there. Such process is ener-
getically favorable and the photogenerated e− and h+ pairs can be
efficiently separated, which is regarded as the key factor for the
enhancement of photocatalytic activities of the ZnO/ZnAl2 O4 com-
posites. Also, it is revealed that the effective design of a coupled
semiconductor composite not only relies on the band structures
of its components, but also is determined by some factors such as
crystallinity, particle size and distribution, as well as loading con-
tent of the active component [44,45]. In this work, the content of
ZnO also shows a significant effect on the photocatalytic activity
of the final ZnO/ZnAl2 O4 composites. As shown in Fig. 7, the pho-
tocatalytic decolorization rate of MO is enhanced gradually at first
but then decreased with increasing the content of ZnO. When the
content of ZnO reaches 25 mol%, the highest decolorization rate of
MO reaches 98.7% within 60 min under simulated sunlight irradia-
tion. While for other samples with ZnO molar ratio of 15% and 35%,
the decoloration rate of MO is 69.6% and 65.3%, respectively. This
phenomenon is interpreted by two reasons. Firstly, the effective
heterojunction with forming good transfer channels to separate
electrons and holes could be formed at the interface between ZnO
and ZnAl2 O4 as the introduction of an appropriate amount of ZnO
into the ZnAl2 O4. The efficient separation of the photogenerated
e− and h+ pairs is regarded as the key factor for the high photo-
catalytic activities. However, when the content of ZnO increases
or decreases to a certain extent, ZnO will reduce the catalytic effi-
ciency of ZnO/ZnAl2 O4 , which is attributed to complete or sparse
coverage of ZnO on the ZnAl2 O4 [46]. It displays low photocatalytic
activity of ZnO or ZnAl2 O4 itself, which can only use about 3–5%
of UV light in sunlight. Secondly, the high photocatalytic activity
of ZnO(25 mol%)/ZnAl2 O4 sample was attributed to higher specific
surface area (Table 1). A larger surface area provides more surface
active sites for the adsorption of reactants molecules, making the
photocatalytic process more efficient [47].
Fig. 8 describes the change in COD value of the reaction solution
under the best degradation conditions. With the increase of reac-
tion time, the COD value decreases. COD of MO solution decreases
by 77% while the degradation rate of MO reached 98.7% within
60 min irradiation, indicating that there are still a certain amount
of organic small molecules in reaction solution.
Fig. 9 shows the photocatalytic activity of the ZnO
(25 mol%)/ZnAl2 O4 sample obtained with varying R and P25.
It can be seen that R has obvious influence on the decolorization
rate of MO. The maximum photocatalytic decoloration rate was
achieved at R = 1, which is slightly higher than that of P25. This
can be ascribed to the formation of regular S@S-ZnO/ZnAl2 O4
structure (Fig. 4c and 4d). The S@S-ZnO/ZnAl2 O4 possess an
unusual nanoporous structure (Fig. 3a), which allows more
244 L. Zhang et al. / Applied Surface Science 268 (2013) 237–245
Fig. 8. COD of reaction solution changes as reaction time. Reaction con-
ditions: 600 ml of reaction solution containing 25 mg L−1 MO and 0.5 g L−1
ZnO(25 mol%)–ZnAl2 O4. .
Fig. 9. Comparison of the photocatalytic activity of P25 and ZnO (25 mol%)/ZnAl2 O4
samples obtained with varying R. (a) R = 0; (b) R = 0.5; (c) R = 1; (d) R = 2; (e) P25.
efficient transport for the reactant molecules to get to the active
sites on the framework walls, hence enhancing the efficiency of
photocatalysis [48]. Moreover, the hollow microspheres allow
multiple reflections of UV–vis light within the interior cavity that
facilitates more efficient use of the light source [49]. However, the
irregular and broken hollow microspheres formed at R = 0.5 and
2 (Fig. 4b and 4e), respectively, which reduced the photocatalytic
activity, suggesting that the activity was enhanced to some extent
by solvent entrapment and sequestration within the enclosed
spheres [28].
4. Conclusion
In summary, a novel S@S-ZnO/ZnAl2 O4 have been fabricated
using glucose as template by a polyethylene glycol (PEG)-assisted
one-pot hydrothermal method and the photocatalytic activity of
the resultant samples has been investigated in detail. The results
showed that the coupling of the ZnO and ZnAl2 O4 enhanced pho-
tocatalytic performance for the photocatalytic decolorization of
MO aqueous solution compared with pure ZnAl2 O4 . Meanwhile,
by adjusting the molar ratio of glucose to metal ion and the con-
tent of ZnO in the final composites led to the high photocatalytic
activity, and the highest decoloration rate of MO reached 98.7%
within 60 min, which exceeded that of Degussa P25 under the same
conditions. The synthesis strategy may provide new design and
controlled fabrication of composite materials with complex hollow
architectures for environmental purification.
Acknowledgements
This work was supported by the National Nature Science Foun-
dation of China (No. 21271071), Natural Science Research Project
of Hunan Province (No. 2012SK3174), and Aid Program for Science
and Technology Innovative Research Team in High Educational
Institutions of Hunan Province.
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