Chemical Engineering Journal 218 (2013) 7380

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Chemical Engineering Journal

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Synthesis, characterization, and visible photocatalytic performance of

Zn2GeO4 nanobelts modied by CdS quantum dots
Xiao-Liang Mao a,b, Dong-Xing Xu a,b, Ming-Lai Fu a,, Baoling Yuan c,, Jian-Wen Shi a, Hao-Jie Cui a
a
Key Laboratory of Urban Environment and Health, Institute of Urban Environment, Chinese Academy of Sciences, No. 1799, Jimei Road, Xiamen, Fujian 361021, China
b
College of Civil Engineering, Fuzhou University, Fuzhou 350108, China
c
College of Civil Engineering, Huaqiao University, No. 668, Jimei Road, Xiamen, Fujian 361020, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

" The rst example of quantum dots to Zn2GeO4 nanobelts modied by CdS quantum dots (Zn2GeO4/CdS) were prepared successfully by chem-
sensitize the photocatalyst of ical bath deposition. The as-obtained samples demonstrated high photocatalytic performance to decolor-
Zn2GeO4. ize dye wastewater under visible light irradiation (k > 400 nm).
" Zn2GeO4/CdS exhibited higher
photocatalytic activity under visible
.
light.
" The composite shows no obvious
deactivation after three recycles
experiments.

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

Article history: Zn2GeO4 nanobelts modied by CdS quantum dots (Zn2GeO4/CdS) were prepared successfully by chem-
Received 7 August 2012 ical bath deposition. The novel photocatalyst was characterized by X-ray diffraction, scanning electron
Received in revised form 16 November 2012 microscopy, X-ray photoelectron spectroscopy and UVVis diffuse reectance spectroscopy. It was found
Accepted 10 December 2012
that Zn2GeO4/CdS consisted of uniform rhombohedral phase Zn2GeO4 nanobelts with highly dispersed
Available online 19 December 2012
cubic phase CdS quantum dots, and the Zn2GeO4/CdS exhibited strong visible light absorption at about
510 nm. The photocatalytic activities of the catalysts were evaluated by the discoloration of Rhodamine
Keywords:
B under visible light illumination and were compared with that of pure Zn2GeO4 nanobelts. The results
Zn2GeO4
CdS
suggested that the composite photocatalyst had much higher photocatalytic activities than pure Zn2GeO4
Photocatalysis nanobelts under irradiation of visible light. Meanwhile, no obvious deactivation of Zn2GeO4/CdS was
Visible light observed after the three recycles experiments in photodegradation of RhB. The possible mechanism of
Rhodamine B visible light photocatalytic degradation is also proposed.
2012 Elsevier B.V. All rights reserved.

1. Introduction in clean energy sources and degradation of environmental pollu-

For past decades, the research of various photocatalytic materi-
als has attracted much attention due to their potential application
Corresponding authors. Tel.: +86 592 6190762; fax: +86 592 6190977 (M. -L.
Fu), tel.: +86 18906015873; fax: +86 592 6162698 (B. Yuan).
E-mail addresses: mlfu@iue.ac.cn (M.-L. Fu), blyuan@hqu.edu.cn (B. Yuan).
tants [13]. Currently, TiO2 is undoubtedly the most widely used
photocatalyst because of its biological and chemical stability,
non-toxicity, cost effectiveness and high activity [46]. However,
it still involved some disadvantages, such as limited activity and
reduced sensitivity to the visible region of sunlight [7]. Therefore,
recently new photocatalysts have been extremely explored that

1385-8947/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2012.12.031
74 X.-L. Mao et al. / Chemical Engineering Journal 218 (2013) 7380
may overcome the limitation of TiO2. To this end, many non-TiO2
photocatalysts were developed with the appropriate band gap
and high quantum yield, such as red P [8], S [9], Ag2CO3 [10],
BiOI/BiOBr [11], Bi2WO6 [12] BiYWO6 [13], GaN [14], V2O5/Al2O3
[15], ZnO/SnO2 [16] and (CuO, Pt)/WO3 [17]. Recently, the Zn2GeO4
has been reported as a promising photocatalyst to degrade organic
pollutant [1820]. Unfortunately, Zn2GeO4 with a wide band gap of
4.68 eV [21,22] still can only response to high-energy UV light. It is
well known that less than 5% of the solar spectrum is UV light. In
contrast, about 45% of the solar spectrum is visible light. Therefore,
the modication of Zn2GeO4 is necessary towards its practical
applications in the environmental and chemical engineering.
Though noble metal has been deposited on the Zn2GeO4 to im-
prove the photocatalysis due to better electronhole separation of
composite under irradiation of UV light [1315,2325], in order to
improve activities more efciently, some promising approaches
have also been developed to tune the visible-light response of Zn2-
GeO4, which include non-metal atom doped [2628]. Coupled with
a smaller band gap semiconductor with a more negative conduc-
tion band (CB) level has been veried as an efcient way to extend
the response of wide band gap semiconductor to visible light [29].
In this way, the charges from the CB of smaller band gap semicon-
ductor can be injected into that of the wide band gap semiconduc-
tor, which could improve the efciency of separation of photo-
generated electronhole pairs as well as the photocatalytic activ-
ity. Until now, a number of quantum dots (QDs), such as CdS
[3033], CdSe [34,35], PbS [36,37], ZnS [38], ZnxCd1xS [39] have
been attempted to sensitize wide band gap semiconductor, such
as TiO2. The response of the resulted composite photocatalyst
can be extended to the visible light and even near infrared light
by this assembly. It was reported that the composites not only
overcome the disadvantages of the individual components but also
induce a synergistic effect, such as reduce of recombination prob-
ability of electrons and holes pairs and enhancement of photosta-
bility [40]. Very recently, we reported the assembly of CdS QDs
onto the TiO2 nanotubes, and the excellent photocatalytic activity
and stability of the composites have been proved [41]. However,
to the best of our knowledge, so far there is no report of any kinds
of QDs to sensitize the photocatalyst of Zn2GeO4. Herein, in order
to extend the response of Zn2GeO4 to visible light, a facile and
straightforward approach has been demonstrated to synthesize
the nanocomposites photocatalyst Zn2GeO4/CdS with Zn2GeO4
nanobelts decorated by CdS QDs employing a sequential chemical
bath deposition (CBD) method. The as-prepared photocatalyst has
been characterized by X-ray diffraction (XRD), scanning electron
microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and
UVVis diffuse reectance spectroscopy (UVVis DRS). The visi-
ble-photocatalytic activity has also been evaluated by use of rho-
damine B (RhB) as a pollutant model. The experiment results
suggested that the CdS QDs dened as cubic CdS phase were
deposited on Zn2GeO4 nanobelts successfully and the Zn2GeO4
nanobelts coupled with CdS QDs showed a high photocatalytic
activity under visible light. Meanwhile, the mechanism of photoca-
talysis of Zn2GeO4/CdS under visible light was also proposed.
2. Material and methods
2.1. Chemicals
GeO2. (P99.999%) and cadmium nitrate tetrahydrate (AR)
were purchased from Aladdin, Zn(CH3COO)22H2O (P99.0%), so-
dium sulde nonahydrate (P98%), rhodamine B (AR) and ethy-
lenediamine (P99.0%) were purchased from Sinopharm
Chemical Reagent. All the reagents are used without any further
purication.
2.2. Synthesis of Zn2GeO4 nanobelts
The Zn2GeO4 nanobelts were prepared using a hydrothermal
synthesis reported previously [24]. In a typical synthesis, GeO2
(0.312 g) and Zn(CH3COO)22H2O (0.66 g, molar ratio of Zn to Ge
is 2:1) were added to mixed solvents comprised of 3 mL deionized
water and 6 ml ethylenediamine. After being stirred (300 r/min)
for 40 min, the mixture was transferred to a stainless Teon-lined
autoclave with 25 mL inner volume. The solvothermal synthesis
was performed under an auto-generated pressure at 180 C for
36 h, followed by cooling to room temperature naturally. The prod-
uct was collected by centrifugation (13800g), washed thoroughly
with deionized water and alcohol several times, and then dried
at 60 C overnight. A white Zn2GeO4 powder was nally obtained
and denoted as ZC-0 (pure Zn2GeO4 nanobelts).
2.3. Deposition of CdS QDs on Zn2GeO4 nanobelts
CdS QDs were deposited on Zn2GeO4 nanobelts employing a
sequential chemical bath deposition (CBD) method. Typically, the
Zn2GeO4 nanobelts were immersed in a solution of Cd(NO3)2
(0.005 M) and sonicated for 5 min, then rinsed with deionized
water until no Cd2+ in supernatant detected, then immersed in a
Na2S (0.005 M) solution (pH = 10.00) for another 5 min followed
by another rinsing with deionized water, and then a yellow prod-
uct was obtained. The ration of Cd2+ to S2 in the preparation of
quantum dot was 1:1. These processes were repeated several times
(5, 10, 15, 20), and the as-prepared samples were named as ZC-5,
ZC-10, ZC-15 and ZC-20, respectively.
2.4. Characterization
XRD patterns were recorded at room temperature with an XPert
Pro diffractometer with Cu Ka irradiation. Diffraction were per-
formed between 20 and 80 with a step width of 0.02 s1. The mor-
phology and structure of the samples were checked by a Hitachi
Model S-4800 eld-emission scanning electron microscope (FESEM)
system. A SEM system equipped for energy-dispersive X-ray (EDX)
spectroscopy was used to determine the composition of the samples.
XPS analysis was conducted on a ESCALAB 250 photoelectron spec-
troscopy (Thermo Fisher Scientic Inc.) at 3.0  1010 mbar with
monochromatic Al Ka radiation (E = 1486.2 eV). UVVis absorption
spectra of various liquid samples were recorded by a UV-2450 spec-
trophotometer (Shimadzu, Japan), and the DRS of the pure Zn2GeO4
nanobelts and Zn2GeO4/CdS with different deposition cycles were
obtained from Shimadzu UV-2450 UVVis spectrophotometer
equipped with an integrating sphere, and the baseline correction
was done using a calibrated sample of barium sulfate.
2.5. Photocatalytic test
The visible-photocatalytic activities of the obtained samples
were investigated by the photodegradation of RhB in an aqueous
solution under atmospheric condition by using a home-made facil-
ity [36,42]. A 500 W tungsten halogen lamp was used as light
source, and positioned at a cylindrical Pyrex vessel, cooled by cir-
culating water when irradiation was performed. The light source
positioned 10 cm from the reaction glassware. Meanwhile, a cut-
off lter was used to remove all light with wavelengths less than
400 nm to ensure irradiation with visible light (Scheme 1). In the
photodegradation of RhB, as-prepared sample (0.10 g) was rst
dispersed in a glass reactor with 100 mL RhB solution (10 mg/L,
pH = 4.8). Prior to irradiation, the suspension was stirred in the
dark for 60 min to achieve an adsorption/desorption equilibrium
between the photocatalyst and RhB solution, and then the suspen-
sion was irradiated to induce photocatalytic reactions. At given
 X.-L. Mao et al. / Chemical Engineering Journal 218 (2013) 7380
Scheme 1. Schematic illustration of the photocatalytic reactor.
irradiation time intervals, 3 mL of the suspension was sampled and
then centrifuged to eliminate the solid particles. The change of RhB
concentration was monitored at the maximum absorbance wave-
length of 554 nm. The percentage of degradation was recorded as
C/C0, in which C is the absorbance of RhB at certain irradiated time
interval and C0 is the absorbance of the initial RhB concentration
when adsorptiondesorption equilibrium was established. The
photocatalytic performance of pure Zn2GeO4 nanobelts was also
tested under the same experimental conditions. When the photo-
catalytic actives of samples under simulated whole light irradia-
tion were investigated, a 500 W Xe lamp was used as light
source instead under the same experimental conditions without
cut-off lter.
The used Zn2GeO4/CdS catalysts were recovered simply by
washing with DI water and the stability of Zn2GeO4/CdS catalysts
was evaluated by photodegradation of a new batch of RhB dye
solution.
3. Results and discussion
3.1. XRD analysis
XRD patterns of the as-prepared pure Zn2GeO4 and Zn2GeO4/
CdS samples with different deposition cycles by CBD method were
shown in Fig. 1. All of the diffraction peaks for Zn2GeO4 nanobelts
can be assigned to the rhombohedral phase of Zn2GeO4 (JCPDS
No.11-0687), with lattice constants of a = b = 14.231 and
c = 9.53 . There is no trace of an impurity phase, such as ZnO
and GeO2 under the instruments resolution. The mechanism of
Zn2GeO4 nanobelts formation is not clear yet [19]. We believe that
the ethylene diamine is crucial in the formation of Zn2GeO4 nano-
belts as no nanobelts products formed in the absence of ED, which
has been reported in the literature [13]. Organic molecule, ED in
this case, is served as a capping reagent in the preparation of
nanomaterials because it can adsorb on solid surfaces and selec-
tively bind to some specic panels to control the velocity and
direction of crystal growth [23], which along the (0 0 1) plane to
grow nanobelts morphology. Compared with the pure Zn2GeO4
nanobelts (ZC-0), the additional peaks appeared in 27.6 and
increasing intensity of diffraction peaks in the region 3035 in
the ZC-10, ZC-15 and ZC-20 can be attributed to cubic CdS phase
(1 1 1) crystal planes (JCPDS No. 80-0019), suggesting that the
deposited CdS with a cubic phase has been successfully deposited.
It is worthwhile to mention that the CdS phase peak intensity in-
crease with an increase of the amount of CdS deposited in the sam-
ples. The diffraction peaks of CdS phase were broad, which
75
x30 Zn2GeO4 JCPDS No. 11-0687
CdS JCPDS No. 80-0019
ZC-20
ZC-15
Intensity (a.u.)
ZC-10
ZC-5
ZC-0
10 20 30 40 50 60 70
o
2 ( )
Fig. 1. The powder XRD patterns of Zn2GeO4 and Zn2GeO4/CdS, and the patterns
ranging from 26 to 30 were enlarged (inset).
indicated that the small crystals size of the deposited CdS QDs on
the surface of the Zn2GeO4 nanobelts. By use of Scherrer equation,
the average sizes of CdS QDs of Zn2GeO4/CdS catalysts were esti-
mated of 4.8, 6.8 and 8.1 nm for samples ZC-10, ZC-15 and ZC-
20, respectively. However, the characteristic peaks of CdS phase
of ZC-5 cannot be discernable, which may be due to the small
amount of CdS attached to Zn2GeO4 nanobelts. These above results
clearly illustrated that the cubic CdS QDs have been successfully
deposited to the Zn2GeO4 nanobelts.
3.2. SEM analysis
The morphologies of the catalysts were observed via SEM.
Fig. 2ac show typical SEM images of the Zn2GeO4 nanobelts and
Zn2GeO4/CdS, respectively. A large quantity of nanobelts with sev-
eral micrometers in length and 30100 nm in width can be seen in
the Fig. 2a and b. Compared with the smooth surface showed in the
Fig. 2a and b, it could be clearly seen in the Fig. 2cd that the sur-
faces of Zn2GeO4 nanobelts were covered with a great amount of
CdS QDs uniformly, indicating that CdS nanoparticles have been
successfully deposited on the surfaces of the Zn2GeO4 nanobelts.
The EDX analysis of ZC-0 and ZC-15 were also performed to deter-
mine the existence of various elements in the as-prepared samples.
As showed from inserted images in Fig. 2d, Cd and S elements were
found to be present in the sample ZC-15, and the atomic ratio of Zn,
Ge, Cd and S is 48.01%, 19.42%, 10.99% and 10.56%, respectively.
The molar ratio of Cd/S is close to 1:1, conrming the stoichiome-
tric formation of CdS QDs. When Cd2+ to S2 ratio was varied in the
deposition, we always found that only CdS nanoparticles were
deposited and the samples of composites are almost the same from
SEM and PRXD as the complete rinsing after each immersion.
Meanwhile, Fig. 3c and d show the corresponding elemental
mapping for elements Cd and S, respectively. These images show
that the elements of Cd and S were uniformly distributed along
the Zn2GeO4 nanobelts, which further prove the successfully depo-
sition of CdS QDs on the surface of Zn2GeO4 nanobelts.
3.3. XPS analysis
In order to conrm the existing CdS on the Zn2GeO4 nanobelts
surface more convincing, XPS analysis was carried out. The result
of XPS analysis (Fig. 4) shows all elements of Zn, Ge, Cd, S and O
are observed, which is consistent with the result of EDX. The Cd
3d5/2 (405 eV) 3d5/2 (412 eV) peaks and S2p peak at 101 eV domi-
76 X.-L. Mao et al. / Chemical Engineering Journal 218 (2013) 7380

Fig. 2. (a, b) FESEM images of Zn2GeO4 nanobelts and (c, d) FESEM images of ZC-15. Insert in (b) and (d): EDX spectra of Zn2GeO4 nanobelts and ZC-15.

Fig. 3. (a, b) SEM images and EDX spectra of the ZC-15, along with the corresponding SEM elemental mapping for (c) Cd and (d) S.
 X.-L. Mao et al. / Chemical Engineering Journal 218 (2013) 7380 77

3.5x10
5
3.5. Photocatalytic activity
Cd3d

3.0x10
5
Zn2p
Fig. 6 shows the photocatalytic degradation of RhB with various
catalyst samples under the visible light. As showed in Fig. 6, the
5 Zn2p Cd3d
2.5x10 Cd3p photodegradation of RhB under irradiation was very slow when
Intensity (a.u.)

Cd3p
no photocatalyst was added (blank in Fig. 6). Also, the photocata-
5 O1s
2.0x10 lytic activity of pure Zn2GeO4 nanobelts can be ignored. On the
contrary, the RhB concentration underwent an obvious decline
5
1.5x10 after 3 h irradiation in presence of Zn2GeO4/CdS, demonstrating
the strong photocatalytic activity of Zn2GeO4 nanobelts modied
5
1.0x10 C1s
by CdS nanoparticles. It was showed in the Fig. 6 that the photocat-
S2p Cd4d
S2s Ge3p
4
alytic activity increased with the increase of CdS deposition cycles,
5.0x10 Zn3pGe3d
and among the four Zn2GeO4/CdS samples, the ZC-15 and ZC-20
performed the highest and lowest visible-light photocatalytic
0.0
1000 800 600 400 200 0
activity, respectively, which are in agreement with the conclusions
Binding Energy (eV) obtained from the UVVis DRS. The reasons may be that excessive
deposition of CdS QDs lead to the complete covering of nanobelts
Fig. 4. XPS pattern of the ZC-15. and larger sizes of CdS QDs, which could decrease the contact be-
tween RhB molecular and nanobelts and lower quantum effect for
nate the spectra of composite. This further indicates uniform CdS
the production of active radicals. In addition the most likely aggre-
QDs deposited on the surface of Zn2GeO4 nanobelts.
gation of CdS QDs occurred could enhance the recombination of
the photoelectrons and holes so as to reduce the photoactivity of
3.4. UVVis diffuse reectance spectroscopy
catalyst [38]. We believe that the causes of different photocatalytic
activities of various photocatalyst might be more complicated and
Fig. 5 shows the UVVis DRS of pure Zn2GeO4 nanobelts and
are most likely the result of the combined action of many factors
Zn2GeO4/CdS with different CdS deposition cycles. It revealed that
[46].
the pure Zn2GeO4 nanobelts (ZC-0) only absorb the UV light of the
Meanwhile, the kinetic model of degradation of RhB by Zn2-
wavelength below about 300 nm, which agrees with those re-
GeO4/CdS under visible light was also investigated. Fig. 7 shows
ported previously [19,24,25], whereas the absorption spectra of
the ln(C0/C) of RhB versus irradiation time t for the different phot-
the Zn2GeO4 nanobelts decorated by CdS QDs were extended into
ocatalysts. The results revealed that the photocatalytic degradation
the visible region (Fig. 5be). The absorption edge of Zn2GeO4/
of RhB by the Zn2GeO4/CdS follows a pseudo-rst-order kinetic
CdS is around 510 nm, indicating that the deposition of CdS highly
law. The rate constants of Zn2GeO4/CdS with different CdS deposi-
enhanced the visible light absorption property of Zn2GeO4/CdS. In
tion cycles were calculated to be 0.005, 0.007, 0.021 and
addition, the absorption of the spectra increased gradually with
0.004 min1 for ZC-5, ZC-10, ZC-15 and ZC-20, respectively. The or-
the deposition cycles of CdS, which could be attributed to in-
der of rate constants was summarized as follows: ZC-15 > ZC-
creased particle size and broadened size distribution of CdS QDs
10 > ZC-5 > ZC-20, which were well agreement with the conclusion
deposited on Zn2GeO4 nanobelts. The similar phenomena can also
of the photodegradation of RhB showed in the Fig. 6. It further
be found in the characterization of TiO2/CdS QDs photocatalyst
illustrated the highest photocatalytic activity of ZC-15. The
[43]. However, the intensity of absorption of ZC-20 decreased obvi-
amounts of RhB adsorbed on various photocatalysts surface prior
ously and was weaker than that of ZC-15. The probable reason of
to photocatalysis were also calculated and the values of ZC-0, ZC-
the phenomenon may be that excessive growth and aggregation
5, ZC-10, ZC-15 and ZC-20 are 8.55%, 7.69%, 16.28%, 15.85% and
of CdS QDs with the increase of deposition cycles [44]. The band
8.12%, respectively. There is no obvious correlation with the photo-
gap energies of Zn2GeO4/CdS were estimated to be 2.43 eV in aver-
catalytic activity can be found in this study. The main reason of dif-
age by calculated according to Eg (eV) = 1240/kg (nm) [45], which is
ferent activities of various photocatalysts may be due to the
much lower than that of pure Zn2GeO4 nanobelts (4.33 eV).

1.0
d
e 1.0
0.8
blank
c 0.8 ZC-0
ZC-5
Absorbance

0.6
ZC-10
ZC-15
0.6
b ZC-20
C/Co

0.4

0.4

0.2
0.2
a
0.0
200 300 400 500 600 0.0
wavelength/nm 0 40 80 120 160 200
t(min)
Fig. 5. UVVis DRS spectra of Zn2GeO4 nanobelts loaded with CdS QDs: (a) ZC-0, (b)
ZC-5, (c) ZC-10, (d) ZC-15 and (e) ZC-20. Fig. 6. Photocatalytic activity of Zn2GeO4/CdS under visible light.
78 X.-L. Mao et al. / Chemical Engineering Journal 218 (2013) 7380

3 1.0

ZC-5
Blank
ZC-10 0.8
ZC
ZC-15 ZC-15
2 ZC-20 0.6

C/C0
ln(C0/C)

0.4

1 0.2

0.0
0 1 2 3 4
Time (h)
0
0 40 80 120 Fig. 9. Photocatalytic decomposition of 2,4,6-Trichlorophenol solution over pure
t/min Zn2GeO4 and Zn2GeO4/CdS under visible light irradiation.

Fig. 7. Plot of ln(C0/C)  t of the photodegradation of RhB by Zn2GeO4/CdS with

different CdS deposition cycles.

different loading of CdS QDs in the surface of Zn2GeO4 nanobelts. 1.0 ZC-0
The highest activity of composite can only be achieved when the ZC-15
proper loading of CdS QDs was deposited in the surface of Zn2GeO4 0.8
nanobelts.
The stability of Zn2GeO4/CdS photocatalyst was tested and the
results are shown in the Fig. 8. As shown, the catalyst still main- 0.6
C/C0

tained a high photocatalytic activity without any descending dur-

ing the photodegradation of RhB even after 3 cycles. It could be
concluded that the Zn2GeO4/CdS was an effective and stable photo-
catalyst for the decomposition of organic pollutants in aqueous
solution.
Another model reaction was chosen, 2,4,6-Trichlorophenol
(TCP), a colorless pollutant with an initial concentration of
50 mg/L replaced RhB to evaluate the photocatalytic activity of
as-obtained Zn2GeO4/CdS under visible light irradiation, and pure
Zn2GeO4 was tested at the same conditions for comparison. As dis-
played in Fig. 9, 2,4,6-Trichlorophenol can hardly be decomposed
under visible light irradiation (k > 400 nm) in the presence of pure
Zn2GeO4, however, it can be decomposed, although slow in com-
parison with RhB, when pure Zn2GeO4 was replaced with the as-
obtained Zn2GeO4/CdS as catalyst. This result further conrms that
the as-obtained Zn2GeO4/CdS has higher visible light-induced
1.0
Circle 1 Circle 2
0.8
0.6
C/C0
0.4
0.2
0.0
0 40 80 120 160 200
t(min)
Fig. 10. Photocatalytic activity of pure Zn2GeO4 and Zn2GeO4/CdS under whole light
irradiation.
photocatalytic activity than pure Zn2GeO4. The different degrada-
tion rate of RhB and TCP may result from the different adsorption
over catalyst, the different substituents and their position in the
aromatic ring of pollutants, and different degradation process.
For the degradation of RhB, the process involved a stepwise de-
ethylation and cleavage of the chromophore ring of RhB [47].
While in the degradation of TCP, the process involved the dechlo-
Circle 3
rination of TCP [48].
The photocatalytic degradation of RhB with different catalyst
samples under the whole light spectrum was also studied. As
shown in the Fig. 10, the photocatalytic activity of ZC-0 is slow,
which only 22.4% of RhB was degraded in 3 h irradiation. On the
contrary, 95.5% of RhB was degraded after 3 h irradiation in pres-

ence of ZC-15, demonstrating the stronger photocatalytic activity

of Zn2GeO4 nanobelts modied by CdS nanoparticles than that of
0.4
the bare Zn2GeO4 nanobelts even under the irradiation of the
whole light spectrum.

0.2
3.6. Mechanism proposed

0.0 In the system of Zn2GeO4/CdS, when the photocatalyst was irra-

0 1 2 3 4 5 6 7 8 9
diated by visible light, CdS QDs can absorb the photons because of
t/h
the lower band gap (2.4 eV), and generate the photoexcited elec-
Fig. 8. Curve of reuse vs. time about photocatalytic degradation of RhB under trons (Eq. (1)) which can quickly transfer from the CB of CdS to that
visible light irradiation. of Zn2GeO4 nanobelts (Eq. (2)) due to the CB position of CdS is high-
 X.-L. Mao et al. / Chemical Engineering Journal 218 (2013) 7380
Fig. 11. Proposed pathways for photocatalysis with Zn2GeO4/CdS.
er than that of Zn2GeO4. As shown in the Fig. 11, the photoexcited
electronhole pairs can be separated quickly, which could prevent
the recombination of electronhole pairs, and lead to the longer
lifetime of the photoexcited electronhole pairs. Then the O2 near
the interface photocatalyst/liquid could be reduced to yield the
superoxide radical anion  O2 and hydrogen peroxide H2O2 (Eqs.
(3) and (4)) by the photoelectrons. The  O
2 and H2O2 can further
interact to produce hydroxyl radical OH (Eq. (5)), which is able
to decompose most organic pollutants in water as a powerful oxi-
dizing specie [13]. Furthermore, the special geometry of Zn2GeO4
nanobelts could enhance the separation of electronhole pairs
[24], which also could improve the photocatalytic activity. It
worthwhile to mention that the photoholes remaining in the va-
lence band (VB) of CdS could not react with hydroxyl groups (or
H2O) around the surface of Zn2GeO4/CdS so that OH radicals can-
not be produced, which can be explained that the VB potential of
CdS is more negative than the redox potential of OH/H2O
(+2.27 eV) [38].
hv
Zn2 GeO4  CdS ! Zn2 GeO4  CdSe h
Zn2 GeO4  CdSe h ! Zn2 GeO4 e  CdSh
e O2 2H ! O
2 3
2e O2 2H ! H2 O2
H2 O2 O  
2 ! OH OH O2
4. Conclusions
In summary, Zn2GeO4/CdS was synthesized by chemical bath
deposition method, and the photochemical property was investi-
gated. The SEM, XRD, XPS and UVVis DRS results demonstrated
the successfully deposition of CdS QDs on Zn2GeO4 nanobelts,
which endow the Zn2GeO4 nanobelts with a strong visible light
absorption at about 510 nm. The as-prepared Zn2GeO4/CdS possess
high efciency for the degradation of RhB solution. The experiment
results also revealed that the Zn2GeO4/CdS have certain reusability
and regeneration performance.
79
Acknowledgments
This work was sponsored by the Xiamen Distinguished Young
Scholar Award (No. 3502Z20126011), the Open Fund of Key Labo-
ratory of Urban Environment and Health, Institute of Urban Envi-
ronment, Chinese Academy of Sciences (No. KLUEH201102), the
National High Technology Research and Development Program
(863 Program) of China (No. 2012AA062606), and the Interna-
tional Science & Technology Cooperation Program of China (No.
2011DFB91710).
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