Zhang 2015

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APSUSC-31001; No. of Pages 11 ARTICLE IN PRESS

Applied Surface Science xxx (2015) xxx–xxx
Contents lists available at ScienceDirect
Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc
Fabrication of TiO2 /MoS2 @zeolite photocatalyst and its photocatalytic

activity for degradation of methyl orange under visible light
Weiping Zhang, Xinyan Xiao ∗ , Lili Zheng, Caixia Wan
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China
a r t i c l e i n f o a b s t r a c t
Article history: TiO2 /MoS2 @zeolite composite photocatalysts with visible-light activity were fabricated via a simple
Received 23 June 2015 ultrasonic-hydrothermal synthesis method, using TiCl4 as Ti source, MoS2 as a direct sensitizer, glycerol
Received in revised form 4 August 2015 water solution with certain dispersion agent as hydrolytic agent, and zeolite as carrier. The structure,
Accepted 6 August 2015
morphology, composition, optical properties, and specific surface area of the as-prepared photocatalysts
Available online xxx
were characterized by using XRD, FTIR, SEM–EDS, TEM, XPS, UV–vis, PL and BET analyzer, respectively.
And the photocatalytic degradation of methyl orange (MO) in aqueous suspension has been employed to
Keywords:
evaluate the photocatalytic activity and degradation kinetics of as-prepared photocatalysts with xenon
TiO2
MoS2
lamp as irradiation source. The results indicate that: (1) TiO2 /MoS2 @zeolite composite photocatalysts
Zeolite exhibit enhanced photocatalytic activities for methyl orange (MO) degradation compared to Degussa
Visible-light P25; (2) photocatalytic degradation of MO obeys Langmuir–Hinshelwood kinetic model (pseudo-first
Photocatalysis order reaction), and its degradation rate constant (kapp ) (2.304 h−1 ) is higher than that of Degussa P25
(0.768 h−1 ); (3) the heterostructure consisted of zeolite, MoS2 and TiO2 nanostructure could provide syn-
ergistic effect for degradation of MO due to the efficient electron transfer process and better absorption
property of TiO2 /MoS2 @zeolite composite photocatalyst.
© 2015 Elsevier B.V. All rights reserved.
1. Introduction photocatalyst could not fulfill the practical application. To enhance

the photocatalytic activities of TiO2 under solar light, multiphase
Solar energy semiconductor photocatalysis, as a potential photocatalyst system has been developed by shifting the wave-
photocatalysis technology, has important research significance for lengths of light the photocatalysts absorb to the visible portion of
solving environmental and energy problems. Numerous attempts the spectrum [5]. Nowadays, significant interest has been devoted
have been made to develop the semiconductor photocatalytic to designing TiO2 -semiconductor multiphase photocatalyst sys-
materials which have wider light absorption range for more effec- tem [6–8], aiming at a synergetic combination of their intrinsic
tively utilizing the solar energy. Titanium oxide (TiO2 )-based outstanding properties and, thus, enhanced performance to meet
nanomaterials are generally considered to be the most reliable requirements imposed by environmental applications, such as
photocatalytic materials for the decomposition of toxic and haz- water purification, detoxification of heavy metal ions. In this area,
ardous organic pollutants. However, TiO2 can absorb only a small All-solid-state Z-scheme photocatalytic systems as a promising
portion of the solar spectrum in the ultraviolet region because composite-type were extensively studied, which has become an
of the wide band gap energy (TiO2 , 3.2 eV), and meanwhile, the important strategy to achieve high-efficiency photocatalyst [9,10].
fast recombination of the photogenerated electron/hole (e− /h+ ) Z-scheme photocatalytic system has a novel photoexcitation mech-
reduces the photonic efficiency and represents the major draw- anism due to its distinctive structure. In TiO2 /CdS Z-scheme system
back of photocatalytic applications [1–4]. So, a single-component (Fig. 1), the electrons of TiO2 and CdS are photoexcited from the VB
to the CB, respectively, leaving the holes in their VB. The electrons
in the CB of TiO2 migrate to VB of CdS through a solid-state elec-
tron mediator, and consume the holes in the VB of CdS. As a result,
Abbreviations: MO, methyl orange; MoS2 , molybdenum dichalcogenides; the electrons and the holes can be completely separated in space,
TiO2 , titanium dioxide; XRD, X-ray diffraction; FTIR, Fourier transform infrared
leading to an enhanced photocatalytic activity of TiO2 /CdS [11].
spectroscopy; SEM, scanning electron microscope; TEM, transmission electron
microscope; PL, photoluminescence; UV–vis, ultraviolet visible.
Molybdenum dichalcogenides (MoS2 ), as a potential semi-
∗ Corresponding author. conductor, has been extensively studied in photocatalysis and
E-mail address: [email protected] (X. Xiao). electrochemical solar energy conversion because of its excellent
http://dx.doi.org/10.1016/j.apsusc.2015.08.054
0169-4332/© 2015 Elsevier B.V. All rights reserved.
Please cite this article in press as: W. Zhang, et al., Fabrication of TiO2 /MoS2 @zeolite photocatalyst and its photocatalytic activity for
degradation of methyl orange under visible light, Appl. Surf. Sci. (2015), http://dx.doi.org/10.1016/j.apsusc.2015.08.054
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2 W. Zhang et al. / Applied Surface Science xxx (2015) xxx–xxx
retains them to be degraded by additional illumination. Zeolites

have high surface area and porous structure, which have been used
as conventional adsorbents. The fine titanium oxide photocata-
lysts loaded on zeolite have opened possibilities for photocatalytic
degradation of various organic pollutants with low concentration
[27,28].
Herein, a novel approach for the synthesis of TiO2 /MoS2 @zeolite
photocatalyst was developed by ultrasonic-assisted hydrothermal
method using micro-MoS2 as the photosensitizer. In this fabrica-
tion process, the formation method of TiO2 /MoS2 contact interface
use bulk MoS2 as the substrate by chemical reaction and followed
by in situ condensation load on the surface of zeolite, and the Z-
scheme TiO2 /MoS2 photocatalyst can be formed on the zeolite.
The morphology, optical property and physical and chemical struc-
tures of TiO2 /MoS2 @zeolite nanocomposites were characterized.
The photocatalytic activities of as-prepared photocatalyst were
evaluated using degradation of methyl orange (MO) under visible-
light irradiation. The photocatalytic degradation mechanism was
also tentatively analyzed.
Fig. 1. Schematic illustration of charge transfer route in the CdS/TiO2 nanocompos- 2. Experimental
ite system.
2.1. Materials
performance such as matching the solar spectrum and stability
against the photocorrosion [12–15]. However, the conduction band
All of the chemicals used for synthesis of the catalysts were of
energy level of bulk MoS2 is less negative than that of TiO2 . Fortun-
analytical grade and were used as-received without any further
ately, nanoscale MoS2 exhibited quantum confinement effects as
purification. Titanium tetrachloride (TiCl4 ), molybdenum disulfide
some research reported [16–19]. Owing to the confinement effects,
(MoS2 , 3 ␮m) and zeolite (20–40 mesh) were obtained from Tian-
the band gap of nanoscale MoS2 can be increased significantly and
jin Fuchen Chemical Reagent Factory (China); Degussa P25 was
the energy level of conduction band is higher than that of TiO2 .
obtained from Evonik Industries (German); ethanol (C2 H5 OH) was
As a graphite-like layered-structure material, commercial MoS2 is
obtained from Nanjing Chemical Reagent Co., Ltd. (China); both
usually the aggregation of three-dimensional multilayer structure,
glycerol (C3 H8 O3 ) and sodium hexametaphosphate ((NaPO3 )6 )
which is bound through Van der Walls force between layers and the
were obtained from Tianjin Kemiou Chemical Reagent Co., Ltd.
multilayer structure MoS2 can be peeled off and formed nanoscale
(China).
structure by using mechanically or chemically exfoliated method
[20,21]. Hence, commercial MoS2 can be used as sensitizer for syn-
thesis of Z-scheme TiO2 /MoS2 photocatalyst. 2.2. Fabrication of TiO2 /MoS2 @zeolite photocatalyst
There are several limitations to use nano-TiO2 with high sur-
face activity as photocatalyst in the photocatalytic reactor. One is First, 4 mL of titanium tetrachloride ethanol solution (TiCl4 ,
fast aggregation of TiO2 in suspension leads to effective surface 2 mol/L) and certain MoS2 powders was added to a beaker, and
area decreased and furthers its catalytic efficiency reduction. Fur- the homogeneous dispersion solution was obtained by ultrasound
thermore, a filtration step after photocatalytic reaction is required method for 10 min at room temperature. Then, 5.6 mL glycerol
because of TiO2 suspension. Attempts have been made to immo- aqueous solution containing certain dispersant as hydrolytic agent
bilize TiO2 on different supports like zeolites [22], clays [23], was added to the dispersion, and the TiO2 –MoS2 vitreosol was
fiberglass [24], activated carbon [25], and carbon nanotube [26]. obtained. Subsequently, the obtained solution vitreosol and cer-
Incorporation of adsorbent into TiO2 has been considered a practi- tain zeolite (based on mass ratio of (TiO2 –MoS2 )/zeolite) were
cal way to enhance the activity. It not only collects pollutants from transferred into 25 mL stainless steel autoclave. The hydrothermal
dilute solution or open air to the vicinity active site of TiO2 , but also synthesis was performed at 413 K for 3 h. TiO2 /MoS2 @zeolite
Fig. 2. Schematic illustration for the preparation of TiO2 /MoS2 @zeolite photocatalyst.
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W. Zhang et al. / Applied Surface Science xxx (2015) xxx–xxx 3
Fig. 3. (A) XRD patterns of TiO2 /MoS2 @zeolite (a), TiO2 @zeolite (b) and zeolite (c); (B) FT-IR spectra of TiO2 /MoS2 @zeolite, TiO2 @zeolite and zeolite.
UV–vis diffuse reflectance spectra were recorded in a Hitachi

UV-3010 spectrophotometer (BaSO4 as a reflectance standard).
Photoluminescence (PL) spectra were measured at room tem-
perature on an F-4500 fluorescence spectrophotometer (Hitachi,
Japan) with an excitation wavelength of 330 nm. The scanning
speed was 1200 nm min−1 , and the PMT voltage was 700 V, and
the width of spectral slit was 2.5 nm.
Nitrogen adsorption isotherms of the samples were achieved
from a 3H-2000PS1 isothermal nitrogen sorption analyzer
(Beishide, China).
2.4. Evaluation of photocatalytic activities
The photocatalytic activities of samples for mineralizing methyl

orange (20 mg/L) were measured as follow: certain as-prepared
powders (125 mg) for degradations of methyl orange was combined
with 250 mL of organic substance solution into a water-cooled reac-
tor and were stirred for 30 min to reach the absorption–desorption
equilibrium in a dark box. Subsequently, the dispersed suspen-
Fig. 4. Raman spectra of TiO2 @zeolite (a) and TiO2 /MoS2 @zeolite (b). sion was irradiated by using XG500 xenon long-arc lamp. At the
given irradiation time intervals (10 min), 4 mL of sample was taken
composite photocatalyst was obtained after separated by cen- out and analyzed by a spectrophotometer (UV-2450, Shimadzu) to
trifuge at 9000 r · min−1 for 5 min, dried at 353 K for 5 h. The record the maximum absorbance (464 nm).
preparation process is shown in Fig. 2.
2.5. Detection of hydroxyl radical (• OH)
2.3. Characterization
The formation of hydroxyl radical (• OH) of as-prepared
The crystal forms of composite photocatalyst was analyzed by materials was detected by a photoluminescence method using
an X-ray diffractometer (D8 Advance, Bruker) with a Cu tube for terephthalic acid (TA) as a probe molecule [29]. 50 mg of as-
generating Cu K␣ radiation (k = 1.5418 Å). prepared sample was dispersed in the aqueous solution (250 mL)
The functional groups of the samples were determined containing 20 mg TA and 20 mg NaOH. Xenon long-arc lamp irradi-
by Fourier Transform-Infrared Spectrometer (FT-IR, Tensor-27, ation was used as visible-light source. 4 mL of reaction solution was
Bruker), in which the IR spectra were recorded by diluting the collected every 15 min for analysis, and then the filtered sample was
milled powders in KBr, and the wavelength between 4000 and used for PL measurement at an F-4500 fluorescence spectropho-
400 cm−1 was used to assess the presence of functional groups in tometer with the excitation wavelength of 321 nm. The scan speed
photocatalyst. was 240 nm min−1 , PMT voltage was 700 V, and the width of exci-
The surface phase compositions of TiO2 @zeolite and tation and emission slit were set to be both 5 nm.
TiO2 /MoS2 @zeolite samples are analyzed by a Raman spectrometer
(LabRAM Aramis, France). 3. Results and discussion
The X-ray photoelectron spectroscopy (XPS) measurements
were performed on a Phi X-tool instrument. 3.1. Structure analysis of the photocatalyst
The morphology, internal structure and composition of the
prepared photocatalysts were observed by a scanning electron Fig. 3A shows the X-ray diffraction patterns of
microscope and energy disperse spectroscopy (SEM: ZEISS Merlin, TiO2 /MoS2 @zeolite (a), TiO2 @zeolite (b) and zeolite (c). The
Germany; EDS: Oxford, England) and transmission electron micro- crystal form of TiO2 in photocatalyst composites is anatase, since
scope (TEM, JEOL, JEM-2100F, Japan). the characteristic diffraction peaks at 25.28◦ , 37.80◦ , 48.05◦ , 53.89◦ ,
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Fig. 5. XPS of TiO2 /MoS2 @zeolite composite: A–Ti 2p, B–O 1s, C–Mo 3d, D–S 2p.
55.06◦ and 62.69◦ (PDF#21-1272) are observed. It reveals that the The FT-IR transmission spectra of TiO2 @zeolite and
crystal of TiO2 is anatase mainly and the rutile is not appeared in TiO2 /MoS2 @zeolite obtained by hydrothermal method treated
this hydrothermal condition. As shown in Fig. 3A(a), the modest at 413 K for 3 h are shown in Fig. 3B. Compared to the Si–O–Si
peaks are appeared at 29.4◦ , 33.0◦ , 38.4◦ , 41.1◦ and 48.1◦ (PDF#17- anti-symmetric stretching vibration of zeolite at the position of
0744), which are corresponding to the characteristic peaks of 1016 cm−1 , that of TiO2 @zeolite and TiO2 /MoS2 @zeolite shows
molybdenite-3R. In addition, there are some apparent peaks at an obvious red shift, which appears 1091 cm−1 and 1084 cm−1 ,
23.01◦ , 42.16◦ , 45.3◦ (PDF#47-1081), which are the diffraction respectively. This is because the sites of Al3+ or Na+ in zeolite are
peaks of MoO3 . MoO3 could be observed mainly owing to parts occupied by several Ti4+ due to the hydrolysis of TiCl4 , which
of MoS2 oxidized in the hydrothermal process. Many research makes the vibration of Si–O changed [32]. The results indicate
results indicated that certain molybdenum oxide exist in photo- the contact interface between zeolite and TiO2 , zeolite and
catalyst systems would enhance the photocatalytic activities of TiO2 /MoS2 connected by the chemical bond. The blue shift for
the photocatalyst system due to their excellent performance in the Si–O–Si of TiO2 /MoS2 @zeolite was observed compared to that
separation of electrons and holes pairs [30,31]. The zeolite charac- of TiO2 @zeolite. Based on quantum size effect, the position of
teristic peaks in TiO2 /MoS2 @zeolite and TiO2 @zeolite composites absorption edge would move to short wave with decreasing the
are appeared at 11.9◦ , 23.6◦ , 27.0◦ and 31.4◦ (PDF#38-0239) particle size, which could be attributed to the coupling of TiO2
corresponding to the diffraction peaks of Faujasite-Na and the and MoS2 . The broadening and strong stretching vibration of
broad peak between 20–35◦ is disappeared compared to pure Ti–O between 798 cm−1 and 471 cm−1 is observed because of
zeolite (see Fig. 3A(c)), which can be boiled down to two reasons the superposition of S···Mo···S at 485 cm−1 and 723 cm−1 , which
as follows: (a) The surface of zeolite has been coated completely indicates the hybrid structure of TiO2 /MoS2 formed on the surface
by the TiO2 /MoS2 or TiO2 nanoparticles, and only few uncovered of zeolite after hydrothermal treatment.
zeolite are exposed to the surface of photocatalyst systems;
(b) the major components of zeolite are aluminosilicate with
3.2. Raman and XPS analysis of the photocatalyst
amorphous form, and their characteristic peak located at 20–35◦ ,
which is covered up by the diffraction peak (25.28◦ ) of anatase
The composition of TiO2 /MoS2 @zeolite and TiO2 @zeolite com-
TiO2 .
posites were investigated by Raman spectroscopy. The unusual
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Fig. 6. SEM images of zeolite (A), TiO2 /MoS2 @zeolite (B) and TEM image of TiO2 /MoS2 (C).
Fig. 7. EDX spectrum of TiO2 /MoS2 @zeolite.
band broadening and the shifting of Raman band have close

relationships with the particle size and phase structure of com- Fig. 8. Formation of TiO2 /MoS2 @zeolite composite in hydrothermal process.
posites. As shown in Fig. 4a, The Raman bands at 153.1 cm−1
(Eg ), 211.5 cm−1 (Eg ), 400.5 cm−1 (B1g ), 515.2 cm−1 (A1g + B1g ),
and 639.2 cm−1 (Eg ) were observed, which were correspond- As compared to the TiO2 @zeolite sample, the 3Eg Raman modes
ing to the active Raman modes of anatase TiO2 [33,34]. For of anatase TiO2 in TiO2 /MoS2 @zeolite sample have red shift. This
the TiO2 /MoS2 @zeolite sample (see Fig. 4b), the anatase TiO2 implies that the vibrational energy was increased owing to the
active Raman modes concluding the 3Eg Raman modes were coupled structure of TiO2 /MoS2 formed on the surface of zeolite.
located at 155.7 cm−1 , 215.0 cm−1 , and 640.1 cm−1 , 2B1g located at Meanwhile, the Raman band at 400.5 cm−1 was divided into three
395.3 cm−1 and 514.7 cm−1 , as well as the A1g located at 514.7 cm−1 . new peak positions of 375.3, 395.3 and 411.8 cm−1 . Among them,
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Table 1
BET specific surface area and average pore size of TiO2 /MoS2 @zeolite, TiO2 @zeolite
and zeolite.
Sample TiO2 /MoS2 @zeolite TiO2 @zeolite Zeolite
SBET (m2 g−1 ) 139.0 261.0 18.5

Average pore size (nm) 9.0 3.3 20.7
the enhancement of adsorption of organic molecule on the sur-

face of photocatalyst and promoting photocatalytic degradation of
organic contaminants.
The energy dispersed spectrum (EDS) reveals the co-existence
of Ti, O, Mo, S, Si and Al, confirming the formation of
TiO2 /MoS2 @zeolite composite (see Fig. 7). Mo and S element
are appeared from the EDS, which show consistency with XRD
and IR results and confirm the existence of MoS2 . This can be
explained that micro-/nano-MoS2 formed has been coated with
nano-TiO2 particles in hydrothermal treatment process, and the
heterostructure about TiO2 /MoS2 is almost embed into the cross-
linked structure of TiO2 , which subsequently loads onto the surface
Fig. 9. Nitrogen adsorption–desorption isotherms of TiO2 /MoS2 @zeolite composite,
of zeolite (see Fig. 8).
TiO2 @zeolite and zeolite. The insert curves were the pore size distribution.
3.4. BET surface area analysis of TiO2 /MoS2 @zeolite

the position of 375.3 cm−1 and 411.8 cm−1 was speculated for the
A1g and E2g1 vibrational modes of MoS , respectively, which are
2 The nitrogen adsorption–desorption isotherms of
consistent with previous results [35,36]. Besides, the modest peak TiO2 /MoS2 @zeolite, TiO2 @zeolite and zeolite exhibit stepwise
located at 204.5 cm−1 was observed, which was attributed to the adsorption behavior as shown in Fig. 9. The BET surface area
Raman mode of MoO3 . The results indicated few MoS2 is oxidized (SBET ) of TiO2 /MoS2 @zeolite is determined to be 139.6 m2 g−1 ,
in fabricating process, which can explain the XRD results. lower than that observed TiO2 @zeolite (261.0 m2 g−1 ), but higher
The surface composition and the valence states of than that of pure zeolite (18.5 m2 g−1 ). The higher specific surface
TiO2 /MoS2 @zeolite photocatalyst were analyzed by XPS mea- area of TiO2 /MoS2 @zeolite and TiO2 @zeolite as compared to pure
surement. The elements of Ti, O, Mo and S are present in the zeolite could be attributed to the accumulation of nano-TiO2 or
survey spectra (see Fig. 5). The characteristic peaks of TiO2 were TiO2 /MoS2 on to the surface of zeolite, leading to the formation
observed at around ∼464.7 eV (Ti 2p1/2 ), ∼459.0 eV (Ti 2p3/2 ) of some new quasi pores or micro-protrude, which significantly
(Fig. 5A) and ∼530.4 eV, ∼531.8 eV (O 1s) (see Fig. 5B). The peaks decreased TiO2 agglomeration to prompt the uniform distribution
at binging energies of ∼233.4 eV and ∼230.2 eV, are observed (see of TiO2 . The pore size analysis shows that the average pore size of
Fig. 5C), which are attributed to the Mo 3d3/2 and Mo 3d5/2 of Mo4+ , TiO2 /MoS2 @zeolite is 9.0 nm (see Table 1), lower than that of pure
respectively. The peak at ∼226.3 eV actually corresponds to the S zeolite (20.7 nm) and larger than that of TiO2 @zeolite (3.3 nm).
2s of MoS2 . As seen in Fig. 5D, the two peaks at binging energies of The TiO2 /MoS2 nanocomposites are formed by the coupling of
∼168.8 eV and ∼165.7 eV could be assigned to the spectra of S 2p1/2 nano-TiO2 and MoS2 on the surface of zeolite, which may lead
and S 2p3/2 for the MoS2 [37,38]. Besides, binding energy of Mo to adhesion and aggregation of TiO2 nanopaticles and produce
3d (236.8 eV) corresponding to Mo6+ is observed, indicating some more mesopores or macropores, and then result in the increase of
molybdenum oxides species formed on the surface of catalysts due average pore size and the reduction of SBET specific surface area
to the oxygen oxidation in the process of materials preparation. on TiO2 /MoS2 @zeolite composites. However, the larger surface
The results indicated the TiO2 /MoS2 formed on the surface of area of heterostructure (TiO2 /MoS2 ) photocatalyst can still provide
zeolite was consisting of TiO2 , MoS2 and MoO3 , which are in more surface active sites for the adsorption of organic pollutant,
agreement with the XRD and Raman results. enhancing the photocatalytic efficiency for the degradation of MO
[39].
3.3. Morphology analysis of the photocatalyst
Fig. 6A and B displays the SEM images of zeolite and 3.5. Optical properties of TiO2 /MoS2 @zeolite photocatalyst
TiO2 /MoS2 @zeolite. As shown in Fig. 6B, the TiO2 /MoS2 com-
posite is uniformly distributed on the surface of zeolite and the The absorbance properties of the as-prepared samples were
rougher surface structure is obtained as compared the pure zeolite measured using UV–vis diffuse reflectance spectroscopy. As illus-
(Fig. 6A), which can obviously increase the adsorbing capacity of trated in Fig. 10A, the zeolite and TiO2 @zeolite has poor absorption
organic molecule and the active sites for the photocatalytic reac- between 400–800 nm. A notable absorption in the visible-light
tion, enhancing the photocatalytic activity of TiO2 /MoS2 @zeolite region between 400–800 nm is observed in TiO2 /MoS2 @zeolite
composite. composite. In addition, the absorption band edges are red-shifted
To further study the morphology structures of TiO2 /MoS2 after doping with MoS2 , which indicates that optical absorption
formed on the surface of zeolite. The as-prepared sample of ability of TiO2 have been improved and the TiO2 /MoS2 compos-
TiO2 /MoS2 @zeolite was distributed by ultrasound method, and ite could be formed on the surface of zeolite after hydrothermal
the cross-link structure of TiO2 /MoS2 was analyzed by TEM. From treatment.
Fig. 6C, the nanopores are observed on the composite, which It has been known that nano-MoS2 can improve the photore-
indicates that TiO2 /MoS2 composite is not to exist as a simple activity of the TiO2 in the visible-light applications. We believe
accumulation on the surface of zeolite but exist as reticulate like that the excellent optical properties of MoS2 have become a favor-
cross-link structure. This special surface structure is beneficial for able electrons-donator for photocatalytic reaction. Fluorescence is
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Fig. 10. UV–vis spectra of TiO2 /MoS2 @zeolite, TiO2 @zeolite and zeolite (A); PL spectra of TiO2 /MoS2 @zeolite and TiO2 @zeolite (B).
Fig. 11. Influence of capacity-loaded of TiO2 /MoS2 (A), dosage of photocatalyst (B) and pH value(C) for degradation of MO; Four cycles of the photocatalytic degradation of
MO catalyzed by TiO2 /MoS2 @zeolite (D).
emitted with the deexcitation of the excited semiconductor materi- the recombination of photoelectrons and vacancies. However,
als. The intensity of the fluorescence collected directly corresponds from another point of view, as one favorable electrons-donator,
to the magnitude of electron–hole pair recombination, in which the MoS2 may do more to increase photogenerated electron
lower fluorescence intensity indicates better photoreactivity with concentration per unit volume, and moreover, lead to the prob-
less deexcitation of electron–hole pairs [40]. PL spectra was ability of electron trapped by oxygen increased [41,42]. In other
obtained by using an F-4500 fluorescence spectrophotometer and words, the high photocatalytic activity of photocatalyst could be
shown in Fig. 10B. Compared to the PL intensity of TiO2 @zeolite, obtained only when the separation rate and capturing electron
the stronger PL intensity was observed on TiO2 /MoS2 @zeolite, rate are faster than recombination rate of photoelectrons and
which indicated that the coupling of TiO2 with MoS2 could increase vacancies.
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Fig. 12. Photocatalytic degradation of MO with TiO2 /MoS2 @zeolite, TiO2 @zeolite, P25 and zeolite (A); −ln(C/C0 )–t relation curves for the photocatalytic degradation of MO
(MO, 20 mg/L; photocatalyst, 500 mg/L) (B).
3.6. Photocatalytic activity of TiO2 /MoS2 @zeolite photocatalyst Table 2

Degradation efficiencies and reaction rate constant for different types of catalysts.
To investigate the photocatalytic activity of TiO2 /MoS2 @zeolite, Sample TiO2 /MoS2 @zeolite TiO2 @zeolite Degussa P25 Zeolite
the degradation of methyl orange (MO) was photo-catalyzed by vis (%) 95.0 77.0 55.0 1.5
TiO2 /MoS2 @zeolite composite under simulated solar-light irradi- kapp (h−1 ) 2.304 0.870 0.768 0.004
ation. As shown in Fig. 11, the influences of capacity-loaded of
TiO2 /MoS2 , dosage of photocatalyst and pH value for the degrada-
tion efficiency of MO is demonstrated, respectively. From Fig. 11A, The photocatalytic reaction kinetics for MO degradation can
the 42.3 wt% TiO2 /MoS2 @zeolite composite holds the optimal per- be expressed by a pseudo-first order reaction equation. The
formance among the five samples and others show varying degrees reaction rate constant (kapp ) is calculated from the intercept
of fluctuation in C/C0 for degradation of MO. This result can be of the plot of −ln(C0 /Ct ) against time t (Fig. 12B), and the
concluded as following reason: the MO absorbed on the surface obtained kapp and degradation rates (vis ) from TiO2 /MoS2 @zeolite,
of TiO2 /MoS2 @zeolite composite appears obvious adsorption and TiO2 @zeolite, Degussa P25 and pure zeolite are shown in
has high degradation rate with increasing the capacity-loaded of Table 2, respectively. TiO2 /MoS2 @zeolite possesses the highest
TiO2 /MoS2 since more active sites will be provided for the degrada- kapp (2.304 h−1 ) for methyl orange (MO) as-compared to that of
tion of MO. It can be known from Fig. 11B, as dosage of photocatalyst TiO2 @zeolite (0.870 h−1 ), Degussa P25 (0.768 h−1 ) and pure zeo-
increased from 0.25 to 0.80 g/L, photocatalytic efficiency gradually lite (0.004 h−1 ), which indicates that the photocatalytic activity of
increased, but when dosage of photocatalyst increased to 1.00 g/L, TiO2 /MoS2 @zeolite surpass the TiO2 @zeolite and Degussa P25 for
photocatalytic efficiency almost remain unchanged. This is because degradation of MO. In addition, the pure zeolite has little degrada-
part of photocatalyst for light utilization is decreased due to light- tion rate and very low reaction rate constant for degradation of
shield effect of superabundant photocatalyst, result in decreasing MO, which indicates the degradation of MO is mainly owing to
photocatalytic efficiency. As a vital factor, PH value has important the adsorption of zeolite. In summarize, the results suggest that
effect on photocatalytic activity of composite. As shown in Fig. 11C, a coupled-structure TiO2 /MoS2 with a positive synergetic effect is
the photocatalytic efficiencies of composite reacting at pH 2 and 7 formed on the surface of zeolite, which apparently improve the uti-
are higher than that of pH 10. Under acid condition, the photocat- lization efficiency of photons. Meanwhile, combining TiO2 /MoS2
alyst can remained preferable dispersibility, which is beneficial to with the absorption properties of organic pollutants onto zeolite,
the absorption and diffusion of dye molecules on catalyst surface small size and homogeneous TiO2 /MoS2 composite distributed on
[43]. In addition, the charge distribution is changed to be beneficial zeolite surface is gained, which leads to a large contact area with
to electron-transfer to surface of photocatalyst, result in increas- organic pollutants, short diffusion time and an enhancement of
ing the separation efficiency of the electron–hole pairs, leading to degradation reaction rate.
the enhancement of photocatalytic activity [44]. The photostability
of TiO2 /MoS2 @zeolite was also discussed in photocatalytic pro- 3.8. Analysis of hydroxyl radicals (• OH)
cess. The photocatalytic cycle experiments were conducted with
the photocatalysts being not recovered and fresh solution of MO In order to understand the relevance between hydroxyl radical
was added into the reactor to undergo the reaction under identi- (• OH) and the optical active of photocatalyst, PL technology was
cal conditions. The degradation rate of MO decreased little after employed with terephthalic acid (TA) as a probe molecule to inves-
four consecutive recycles, indicating the better photostability of tigate the • OH generated on the surface of the photocatalyst. The
TiO2 /MoS2 @zeolite, from Fig. 11D. terephthalic acid interact with • OH to form highly fluorescent 2-
hydroxy terephthalic acid [45]. The PL emission spectra excited
3.7. Photocatalytic dynamics for MO degradation at 321 nm from TA solution are measured every 15 min of illu-
mination. Fig. 13 gives the plots of the fluorescence intensities at
Fig. 12 illustrates the photocatalytic degradation rate and 427 nm along with the irradiation time of TiO2 /MoS2 @zeolite and
kinetics of TiO2 /MoS2 @zeolite photocatalyst comparison with TiO2 @zeolite. For the TiO2 @zeolite composites, the PL intensity
TiO2 @zeolite, Degussa P25 and pure zeolite. Degussa P25 with gradually increases with the irradiation time due to the excita-
the mixed anatase and rutile phases has been widely used as tion of TiO2 particles under simulate solar irradiation. Under the
the referred photocatalyst for photocatalytic activity evaluation. irradiation, the MoS2 can be easily photoexcited due to the lower
G Model
Fig. 13. PL spectra change of terephthalic acid in different time for • OH captured experiment of TiO2 /MoS2 @zeolite (A) and TiO2 @zeolite (B). The insert images are the PL
intensity changing with time.
Fig. 14. Effects of scavengers on the degradation of MO (irradiation time = 60 min,

Fig. 15. Schematic diagram of photocatalytic mechanism and the photogenerated
scavenger dosage = 0.1 mmol L−1 ).
charge-transfer process in TiO2 /MoS2 composite.
photoexcited energy, implying the better utilization of the pho-

alcohol, silver nitrate and EDTA-2Na are added into the reaction
ton. So compared to the PL spectra of TiO2 @zeolite (Fig. 13B), the
system, the degradation rate was 13.1, 60, 70 and 96%, respectively,
TiO2 /MoS2 @zeolite (Fig. 13A) has the higher fluorescence inten-
which indicates the important role of superoxide radical on the
sity per unit time in the trapping • OH process, which indicates the
elimination of MO [49,50], while the • OH and free electron also
enhancement of photocatalytic activity of TiO2 /MoS2 @zeolite. It
have implications for the degradation of MO, but the h+ seem to be
indicated that a coupled-structure of TiO2 /MoS2 with synergistic
negligible in the reaction.
effect could be formed on the surface of zeolite, which significantly
Under the simulated solar-light irradiation, the mechanism
enhances utilization efficiency of quantum photon and separation
of active species generation can be described according to
efficiency of electron/hole pairs under visible-light irradiation. The
the Z-scheme electron-transfer mechanism in TiO2 /MoS2 @zeolite
electron generated from nano-MoS2 is captured by the absorbed O2
[5,10,11]. As shown in Fig. 15, the photogenerated electrons and
to form • O2 − , which may lead to the enhancement of photocatalytic
holes are accumulated in the CB of MoS2 and VB of TiO2 , respec-
activity of TiO2 /MoS2 @zeolite for the degradation of MO.
tively. The EBCB (BCB: the bottom of the conduction band) of MoS2
is more negative than the redox potential of O2 /• O2 − . The photo-
3.9. Analysis of active species and possible photocatalytic generated electrons in the CB of MoS2 can reduce the absorbed O2
mechanism for MO degradation into • O2 − . Besides, the ETVB of TiO2 (TVB: the top of the valence
band) is more positive oxidation potential than that of • OH/OH− .
In order to investigate the photocatalytic mechanism and This suggests that the • OH can be easily produced in the VB of TiO2 .
the influence of active component generated during the cat- However, the visible light was the main energy of available photon
alytic process of TiO2 /MoS2 @zeolite composite, benzoquinone, under simulated solar irradiation, implying that few photons can
tert-butyl alcohol, silver nitrate and EDTA-2Na were employed be effectively utilized by TiO2 . Hence, few • OH are produced by a
as the scavengers of superoxide radical (• O2 − ), hydroxyl radical single-component of TiO2 , which is agreement with the obtained
(• OH), electron (e− ) and hole (h+ ) [46–48]. Different scavengers are experimental results.
employed individually to remove the corresponding active species So the photocatalytic degradation of MO can be summarized by
so that the function of different active species in the degradation the following mechanism reactions.
process is understood. As shown in Fig. 14, the degradation rate
of MO is 95% without scavengers. When benzoquinone, tert-butyl MoS2 (nanoscale) + hv → MoS2 (eCB − + hVB + ) (1)
G Model
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APSUSC-31001; No. of Pages 11 ARTICLE IN PRESS

Contents lists available at ScienceDirect

Applied Surface Science

Fabrication of TiO2 /MoS2 @zeolite photocatalyst and its photocatalytic

1. Introduction photocatalyst could not fulﬁll the practical application. To enhance

retains them to be degraded by additional illumination. Zeolites

UV–vis diffuse reﬂectance spectra were recorded in a Hitachi

2.4. Evaluation of photocatalytic activities

The photocatalytic activities of samples for mineralizing methyl

Fig. 7. EDX spectrum of TiO2 /MoS2 @zeolite.

band broadening and the shifting of Raman band have close

Sample TiO2 /MoS2 @zeolite TiO2 @zeolite Zeolite

SBET (m2 g−1 ) 139.0 261.0 18.5

the enhancement of adsorption of organic molecule on the sur-

3.4. BET surface area analysis of TiO2 /MoS2 @zeolite

3.6. Photocatalytic activity of TiO2 /MoS2 @zeolite photocatalyst Table 2

Fig. 14. Effects of scavengers on the degradation of MO (irradiation time = 60 min,

photoexcited energy, implying the better utilization of the pho-

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