1. Applied Catalysis A: General 407 (2011) 224–230
Contents lists available at SciVerse ScienceDirect
Applied Catalysis A: General
journal homepage: www.elsevier.com/locate/apcata
Toluene decomposition using silver vanadate/SBA-15 photocatalysts: DRIFTS
study of surface chemistry and recyclability
Wen-Sheng Chang a , Yu-Chu M. Li b , Tsair-Wang Chung c , Yung-Sen Lin d , Chao-Ming Huang e,∗
a
Green Energy & Environment Research Labs, Industrial Technology Research Institute, Hsinchu, Taiwan
b
Department of Mechanical Engineering, Southern Taiwan University, Tainan, Taiwan
c
Department of Chemical Engineering/R&D Center for Membrane Technology, Chung Yuan Christian University, Taoyuan, Taiwan
d
Department of Chemical Engineering, Feng Chia University, Taichung, Taiwan
e
Department of Materials Engineering, Kun Shan University, Tainan, Taiwan
a r t i c l e i n f o a b s t r a c t
Article history: Silver vanadate (SVO) containing SBA-15 visible-light-driven photocatalyst was synthesized using the
Received 13 May 2011 incipient wetness impregnation procedure. X-ray diffraction (XRD) results reveal that the SVO/SBA-15
Received in revised form 27 August 2011 powders consisted of three kinds of phase: pure Ag4 V2 O7 or pure ␣-Ag3 VO4 or mixed phases of Ag4 V2 O7
Accepted 29 August 2011
and ␣-Ag3 VO4 . The mass spectra indicate that the main oxidation intermediate of toluene is benzalde-
Available online 3 September 2011
hyde. The sample loaded with 51 wt% SVO (51SVO/SBA-15) exhibited the best photocatalytic activity. The
results of two consecutive cyclic runs and regeneration indicate that the accumulation of benzaldehyde
Keywords:
causes an irreversible deactivation of P25, but no deactivation of 51SVO/SBA-15. The enhanced photo-
SBA-15
Visible-light-driven photocatalyst
catalytic activity of 51SVO/SBA-15 is attributed to mixed crystalline phases of Ag4 V2 O7 and ␣-Ag3 VO4 ,
Toluene photo-oxidation where ␣-Ag3 VO4 is the major component. In situ diffuse reflectance infrared Fourier transform spec-
Brønsted and Lewis acids troscopy (DRIFTS) confirms the presence of Brønsted and Lewis acids on the SVO/SBA-15 composites. A
favorable crystalline phase combined with high intensities of Brønsted and Lewis acids is considered the
main cause of the enhanced adsorption capacity, outstanding photoactivity, and long term stability of
the SVO/SBA-15 composites.
© 2011 Elsevier B.V. All rights reserved.
1. Introduction devoted to loading TiO2 species onto or incorporating them into the
mesoporous silica called Santa Barbara Amorphous-15 (SBA-15) to
Volatile organic compounds (VOCs), extensively used as sol- combine adsorption and photocatalysis for the rapid removal of
vents, aerosol propellants, and raw materials, are considered as VOCs [1–4]. However, the use of titania-SBA-15 composites is hin-
great contributors to atmospheric pollution, with some consid- dered by some major shortcomings. First, TiO2 has low efficiency
ered toxic. Due to increasing eco-awareness, regulations set by of degrading VOCs under visible-light illumination due to its wide
governments regarding the emission of VOCs have grown stricter. band gap, which is in the range of 3.0–3.2 eV. Second, the most
The most conventional reduction method of VOCs is adsorption general method for synthesizing TiO2 is the sol–gel method, which
technology, which transforms air pollutants into another phase, requires high-temperature calcination (673 K or higher) to obtain
creating secondary pollution. Since the adsorption of VOCs does good crystallinity. Moreover, the reaction intermediates can be in
not actually destroy the pollutants, the regeneration of adsorbents some cases more toxic and/or stable than the parent VOC during
is a problem after saturation. Among the available alternatives the PCO process. Therefore, the development of visible-light-active
to adsorption, photocatalytic oxidation (PCO) is quite promising photocatalysts that can minimize the amount of intermediates dur-
for VOC reduction as it has the potential to completely mineral- ing the photocatalytic process is desirable.
ize VOCs to CO2 and H2 O, which may meet the requirements of The present work demonstrates the preparation of silver
more stringent VOC emission control in the future. A vast number vanadate/SBA-15 composites (SVO/SBA-15) via hydrothermal syn-
of studies related to titanium dioxide, a UV-active photocatalyst, thesis using a post-synthesis step without high-temperature
have been conducted. Recently, a lot of research effort has been calcination. The photodecomposition of toluene was selected as a
model reaction because toluene is a common atmospheric indoor
and industrial air pollutant. Toluene has usually shown high ini-
∗ Corresponding author at: 949 Da-Wan Rd., Yung-Kang Dist., Tainan 71003, tial conversions followed by very low steady-state conversions,
Taiwan. Tel.: +886 6 2050530; fax: +886 6 2050493. which has been attributed to catalyst deactivation during the PCO
E-mail address: charming@mail.ksu.edu.tw (C.-M. Huang). process [5]. In order to determine the stability of the SVO/SBA-15
0926-860X/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2011.08.043

2. W.-S. Chang et al. / Applied Catalysis A: General 407 (2011) 224–230 225
composites, the recyclability test of the SVO/SBA-15 composites were calculated using the Brunauer–Emmett–Teller (BET) method
was investigated using DRIFTS. in the relative pressure range of 0.06–0.2. The pore size distri-
butions were determined from the analysis of the adsorption
isotherm using the Barret–Joyner–Halenda (BJH) algorithm. The
2. Experimental procedure
total pore volumes were estimated from the adsorbed N2 amount
at P/P0 = 0.973.
2.1. Preparation of photocatalyst
2.3. Photocatalytic activity evaluation with GC–MS and DRIFTS
SBA-15 was synthesized with Pluronic P123 (EO20 PO70 EO20 ,
Mav = 5800; Aldrich) and tetraethylorthosilicate (TEOS) according
The photocatalytic oxidation of toluene was performed in situ
to a previous report [6]. Briefly, 4.0 g of P123 was dissolved in 30 g
in an IR cell with ZnSe windows. An LED lamp, with a wave-
of de-ionized water and 120.0 g of HCl solution (2 M) with stirring at
length ranging from 430 to 620 nm with a photon intensity of
313 K for 2 h. Then, 8.5 g of TEOS was added into the P123 solution,
4 mW/cm2 , was used as the visible-light source [8]. A gaseous
which was stirred for another 22 h until a white gel precipitated.
toluene/N2 mixture was generated, corresponding to the target
The gel was transferred to a Teflon bottle and heated at 403 K for
toluene concentration of 200 ppmv. Prior to the experiments, the
24 h. The precipitate was filtered, washed several times with de-
samples were pre-treated by heating and flushing with N2 flow
ionized water, dried overnight at 373 K, and then calcined at 773 K
(20 ml/min) from room temperature to 523 K, held at 523 K for
(heating rate of 1 K/min) for 4 h in air.
30 min, and then cooled to 303 K. The procedure for all PCO experi-
The silver-vanadate-loaded SBA-15 (SVO/SBA-15) was prepared
ments was as follows: (1) toluene/N2 flow was introduced into the
via the incipient wetness impregnation procedure. In the prepara-
photoreactor at a constant flow rate of 20 ml/min; (2) when the
tion process, 0.204 g AgNO3 was dissolved in urea aqueous solution
photoreactor inlet and outlet toluene concentrations were approx-
(120 g H2 O, 0.577 g urea) with stirring at room temperature for 0.5 h
imately equal, the LED lamp was turned on and the toluene/N2
to obtain solution A. Solution B was prepared by mixing 0.047 g
flow was stopped; (3) the photoreactor was flushed with the N2
NH4 VO3 with 0.3 g SBA-15 in de-ionized water at 343 K for 1 h
flow at 5 ml/min for 30 min, and then the N2 flow was stopped.
under an ultrasonic bath. A suspension formed when solution A was
The gaseous products (intermediates) were analyzed on-line by
added dropwise to solution B under vigorous stirring for 1 h. The
GC–MS. GC–MS analyses were carried out on a gas chromato-
molar composition of the suspension AgNO3 /NH4 VO3 /CO(NH2 )2
graph (GC, Perkin-Elmer, Clarus 500) using a 60-m DB-624 capillary
was 3.0/1.0/12.0. The suspension was titrated to pH 7 using ammo-
column, coupled with a quadrupole mass spectrometer (MS, SRS,
nia solution, followed by additional stirring at room temperature
QMS 300) at regular intervals. The spectra of the adsorbed species
for 24 h. Finally, the as-obtained suspension was transferred into
on the catalyst surface were recorded under both darkness and
a Teflon-lined autoclave with hydrothermal treatment (temper-
illumination. The spectra of the catalyst and the reaction intermedi-
ature: 413 K, time: 4 h). After the hydrothermal procedure, the
ates during the reaction were expressed in units of Kubelka–Munk
resulting precipitates were collected and washed with de-ionized
(K–M).
water three times, and then dried at 353 K for 12 h. These samples
were denoted xSVO/SBA-15, where x represents the weight per-
2.4. DRIFT characterization of NH3 species
centage of silver vanadate (wt%). The sample synthesized under
identical conditions without the addition of SBA-15 was denoted
To determine the types of acid site present on the sam-
SVO.
ples, temperature-programmed desorption of ammonia (NH3 ) was
carried out using DRIFT. Ammonia usually provides the probe
2.2. Sample characterization molecules in spectroscopic experiments to determine the type of
acid site in heterogeneous catalysis: Brønsted sites or Lewis sites.
The X-ray diffraction (XRD) patterns of the powders were mea- Prior to the experiments, the samples were heated in situ from
sured using an X-ray diffractometer (PANalytical X’Pert PRO) with room temperature to 523 K at 10 K/min in N2 flow (30 ml/min),
Cu radiation ( = 0.15418 nm) in the 2Â range of 20–60◦ . High- held at 523 K for 30 min, and then cooled down to 303 K. The sam-
resolution transmission electron microscopy (HRTEM) images of ples were saturated at 303 K with a gas mixture of 5% NH3 in N2
the samples were observed on a Philips Tecnai G2 F20 micro- (30 ml/min) for 30 min. At the end of the saturation process, the
scope equipped with energy-dispersive X-ray spectroscopy (EDX) samples were flushed with N2 flow (30 ml/min). Then, the sam-
operated at an accelerating voltage of 200 kV. Photoluminescence ples were heated again at a heating rate of 10 K/min from 30 K to
(PL) spectra were recorded by a fluorescence spectrophotome- 523 K and held at 523 K for 60 min. The DRIFT spectra with a reso-
ter (Dongwoo, Optron) under excitation at 325 nm. In situ lution of 4 cm−1 were collected in the interval of 1200–1700 cm−1
DRIFTS measurements were performed using a FTIR spectrome- for determining surface acidity.
ter (PerkinElmer, Spectrum GX) and a diffuse reflectance accessory
(Harrick Scientific, DRP-PE 9) with a temperature- and atmosphere- 3. Results and discussion
controlled high-temperature low-pressure reaction cell (Harrick
Scientific, HVC-DRP 3). Prior to the IR measurements, the sam- 3.1. X-ray diffraction analysis
ples were dehydrated under vacuum from room temperature
to 523 K at 10 K/min in N2 flow (30 ml/min), held at 523 K for The XRD patterns of SVO and SVO-SBA-15 are shown in Fig. 1.
30 min, and then cooled to 303 K. DRIFT spectra with a resolu- Fig. 1a shows the low-angle XRD patterns of SBA-15 and SVO/SBA-
tion of 4 cm−1 were collected in the interval of 2800–4000 cm−1 15 samples. The XRD pattern of SBA-15 shows three well resolved
for surface hydroxyl functional groups [7]. The surface area and peaks: a sharp peak at 1.0◦ and two weak peaks near 1.5◦ and
pore volume of the as-prepared samples were determined using 2.0◦ , respectively, which can be indexed to (1 0 0), (1 1 0), and
a volumetric sorption analyzer (Micromeritics, ASAP 2020). The (2 0 0) reflections of an ordered hexagonal P6mm space group,
samples were degassed at 473 K under vacuum conditions for a respectively. For SVO/SBA-15 samples, the XRD peaks decreased in
period of at least 4 h prior to measurements. The nitrogen adsorp- intensity, which was probably caused by the decreasing scatter con-
tion/desorption isotherms were measured over a relative pressure trast between pore walls and the pore space with the introduction
(P/P0 ) range of approximately 10−3 to 0.995. The surface areas of SVO. For the samples with high SVO content, the intensities of the

3. 226 W.-S. Chang et al. / Applied Catalysis A: General 407 (2011) 224–230
Fig. 2. N2 adsorption–desorption isotherms of SBA-15 and SVO/SBA-15 samples.
silver vanadates were increased to 60 and 70%, all peaks attributed
to ␣-Ag3 VO4 disappeared and pure Ag4 V2 O7 was observed.
3.2. Porosity and surface area characterization
Fig. 2 shows the nitrogen adsorption-desorption isotherms of
SBA-15 and SVO/SBA-15 samples. The N2 adsorption–desorption
isotherms of SBA-15 show type IV adsorption with a H1 hysteresis
loop, indicating a mesoporous characteristic. For the SVO/SBA-15
samples, a sharp inflection in the relative pressure (P/P0 ) range
of 0.65–0.95, corresponding to capillary condensation within uni-
form mesopores, was observed. Compared to SBA-15, the capillary
condensation of SVO/SBA-15 shifted to higher relative pressure,
indicating an increase of the pore diameter when SVO was loaded
into/onto SBA-15. The textural properties of SBA-15 support and
SVO/SBA-15 samples are listed in Table 1. It can be seen that
the specific surface area and pore volumes of SVO/SBA-15 sam-
ples significantly decrease with increasing silver vanadate loading,
whereas the pore diameter increases. When the SVO/SBA-15
samples were synthesized using a post-synthesis method, the
silver and vanadate species reacted on the surface of SBA-15;
thus, the BET surface and pore volumes of SVO/SBA-15 com-
posites decreased with increasing amount of SVO. The average
pore diameter increased for SVO/SBA-15, which might be due to
the small pores of SBA-15 being obstructed by silver vanadate
nanoparticles.
3.3. Morphology
Fig. 1. (a) Low-angle and (b) wide-angle XRD patterns of SVO and SVO/SBA-15.
To better understand the formation of SVO nanocrystals on the
mesopores and explore the effect of SVO on the pore structure of
SVO/SBA-15 photocatalyst, HRTEM images were recorded. HRTEM
peaks are much weaker but can still be discerned, demonstrating
that the uniform porous structure of SBA-15 is retained. The unit-
Table 1
cell parameter (a0 ) of SVO/SBA-15 catalysts (ca. 13.0–14.0 nm) is Specific surface areas and pore properties of P25, SVO, SBA-15, and SVO/SBA-15.
larger than that of SVO (11.8 nm). This may be ascribed to the partial
Sample SBET (m2 g−1 ) Pore volume Pore size
incorporation of SVO into the framework of SBA-15. Fig. 1b shows
(cm3 g−1 ) (nm)
wide-angle XRD patterns of SVO/SBA-15 samples and SVO. As can
be seen, the SVO and SVO-SBA-15 samples have three kinds of P25 56 0.25 17.52
SVO 2 0.002 7.30
XRD patterns, assigned to the pure Ag4 V2 O7 , to the pure ␣-Ag3 VO4 , SBA-15 787 1.09 7.61
and to the mixed phases of Ag4 V2 O7 and ␣-Ag3 VO4 , respectively. 17SVO/SBA-15 193 0.70 14.90
The pure SVO and 51SVO-SBA-15 samples had mixed phases of 34SVO/SBA-15 141 0.54 16.14
␣-Ag3 VO4 and Ag4 V2 O7 . When the weight percentages of silver 51SVO/SBA-15 99 0.35 15.32
60SVO/SBA-15 96 0.34 13.61
vanadates were lower than 51%, pure ␣-Ag3 VO4 was obtained for
70SVO/SBA-15 85 0.33 15.86
17 and 34SVO/SBA-15 samples. When the weight percentages of

4. W.-S. Chang et al. / Applied Catalysis A: General 407 (2011) 224–230 227
Fig. 3. HRTEM images of (a) SBA-15 and (b) 51SVO/SBA-15.
images of SBA-15 and 51SVO/SBA-15 samples are shown in Fig. 3. 3.4. Adsorption and photocatalytic oxidation of toluene
The highly ordered mesoporous channel structure of pure SBA-15
can be observed in Fig. 3a, which shows a pore diameter of around The adsorption and photodegradation curves of gaseous toluene
7–8 nm, in agreement with N2 adsorption–desorption results. Due over samples were shown in Fig. 5. Prior to photocatalytic exper-
to the electronic density contrast of TEM, clear and gray stripes can iments, the concentration of gaseous toluene rapidly decreased
be observed between empty channels and silica walls. When the during the initial 10 min, which was due to the adsorption of
SVO loading was increased to 51 wt% (Fig. 3b), the ordered array of toluene on catalyst surface. After 30 min, the concentration of
mesopores remained intact. Silica walls remained white whereas gaseous toluene is increased to the initial state, indicating that the
the SVO particles, with a larger electronic density, turned black. The adsorption of toluene reaches equilibrium. In the absence of irradi-
morphology results indicate that nanocrystalline SVO was inserted ation, the as-prepared SVO/SBA-15 composites except 17SVO/SBA-
into the mesoporous channels of SBA-15 when urea was used as 15 exhibit a much higher adsorption capability of toluene than
the chelating agent, which indicates a strong interaction between those of SVO and P-25. The toluene adsorption capacity is thus
urea and metal ions that prevents the precipitation of silver and affected by the silver vanadate content of SVO/SBA-15 composites.
vanadium ions before the formation of silver vanadate–silica com- It is well known that photocatalytic oxidation of organic pollu-
posites. EDX elemental analysis of a selected point of SBA-15 and tants in the initial stage follows Langmuir–Hinshelwood kinetics;
the SBA-15 supported catalyst (Fig. 3) confirms the presence of the L–H model can be simplified to a pseudo-first-order expres-
SVO particles in the center of a SBA-15 channel. Fig. 4 shows sion: ln(Ce /C) = kt (where Ce and C are the equilibrium concentration
SEM images for SBA-15 support and SVO/SBA-15 composites. SEM of adsorption and the concentration of VOC at the exposure
image (Fig. 4a) of parent SBA-15 sample presents well-defined time, t, respectively, and k is the apparent rate constant). The
sausage-like particles of approximately 1.5 ␮m in length. These calculated kapp of toluene decreased in the order: 51SVO/SBA-
sausage-like particles cluster together to form rope-like aggregates, 15 (0.032 min−1 ) > 34SVO/SBA-15 (0.024 min−1 ) > 60SVO/SBA-15
which are parallel straight mesochannel arraying along the long (0.020 min−1 ) > 70SVO/SBA-15 (0.019 min−1 ) > SVO (0.018 min−1 )
axis. The SEM images in Fig. 4b–d demonstrate that the ordered > 17SVO/SBA-15 (0.016 min−1 ) > P25 (0.015 min−1 ).
rope-like domains are preserved after silver-vanadate impregna- The evolution of gaseous benzaldehyde as a function of irra-
tion for 17, 34, and 51SVO/SBA-15 samples. On the other hand, 60 diation time was plotted in Fig. 6. During the first 10 min of
and 70SVO/SBA-15 samples show the presence of an overgrowth toluene photodegradation, the amounts of benzaldehyde pro-
as the irregular ragged particles when high amounts of silver- duced for all SVO/SBA-15 samples were higher than those of
vanadate nanoparticles are deposited (Fig. 4e and f). However, the SVO and P25. However, at longer reaction times, the amount
stacked nanoparticles do not lead to any significant change in the of benzaldehyde generated for 17SVO/SBA-15 is lower than
morphology of silica. that of SVO. The amount of benzaldehyde decreased in the

5. 228 W.-S. Chang et al. / Applied Catalysis A: General 407 (2011) 224–230
Fig. 4. SEM images of various SBA-15 samples: (a) parent SBA-15, (b) 17SVO/SBA-15, (c) 34SVO/SBA-15, (d) 51SVO/SBA-15, (e) 60SVO/SBA-15, and (f) 70SVO/SBA-15.
following sequence: 51SVO/SBA-15 > 34SVO/SBA-15 > 60SVO/SBA- It is well known that the adsorption capacity is mainly deter-
15 > 70SVO/SBA-15 ∼ SVO > 17SVO/SBA-15 > P25. A big degree of mined by the specific surface area and nature of the surface of
photodegradation of toluene takes place in case of 51SVO/SBA- the photocatalyst. Studies have shown that the much higher spe-
15. Generally speaking, photocatalytic activity is related to the cific surface area and pore volume of TiO2 -containg mesoporous
crystalline phase. Konta et al. [9] reported that ␣-Ag3 VO4 showed silica composites compared to those of pure titania are benefi-
stronger photocatalytic activity than those of ␤-AgVO3 and cial for the adsorption of organic pollutants [13–15]. As shown
Ag4 V2 O7 for O2 evolution from an aqueous silver nitrate solu- in Fig. 5, 51SVO/SBA-15 exhibited the highest adsorption capac-
tion under visible-light irradiation. For the SVO/SBA-15 series, it ity of toluene instead of 17SVO/SBA-15. However, 17SVO/SBA-15
was observed that the 51SVO/SBA-15 sample, with mixed phases had much higher specific surface area and pore volume than those
of ␣-Ag3 VO4 and Ag4 V2 O7 , exhibits the highest photocatalytic of 51SVO/SBA-15; therefore, the toluene adsorption capacity is
activity, whereas 34SVO/SBA-15 shows lower activity than that of thus greatly influenced by the silver vanadate content, rather
51SVO/SBA-15 even though 34SVO/SBA-15 has a high crystallinity than the specific surface area. To further characterize the sur-
of ␣-Ag3 VO4 . An increasing number of studies have indicated that face attributes that affect toluene adsorption, the surface acidity,
a bicrystalline framework of anatase and rutile show much better the existence of Brønsted and Lewis acid sites, of the samples
photocatalytic activity than that of pure anatase TiO2 [10–12]. was examined using DRIFTS to detect ammonia adsorption on

6. W.-S. Chang et al. / Applied Catalysis A: General 407 (2011) 224–230 229
Fig. 5. Time-dependent concentrations of gaseous toluene in the dark and under Fig. 8. Normalized PL intensity of the samples measured at 300 K.
visible light.
vanadate surfaces is supported by the presence of a band at
1425 cm−1 due to the asymmetric deformation mode [16–18]. The
band at 1604 cm−1 is assigned to NH3 coordinately bonded to
Lewis acid sites [19–21]. It can be concluded that both Brønsted
and Lewis acid sites exist on the surfaces of SVO and SVO/SBA-15.
The intensities of Brønsted and Lewis acid sites, detected at 1425
and 1604 cm−1 , respectively, follow the sequence: 51SVO/SBA-
15 > 34SVO/SBA-15 > 17SVO/SBA-15 ∼ SVO. The trend of Brønsted
and Lewis acid sites is in agreement with that of the adsorp-
tion capacity. That is, higher intensities of Brønsted and Lewis
acids of silver vanadate indicate a larger adsorption capacity for
toluene.
3.5. Photoluminescence spectra
Fig. 6. Time-dependent concentrations of gaseous benzaldehyde during toluene PL spectra have been widely used to disclose the migra-
photocatalytic degradation with P25, SVO, and SVO/SBA-15. tion, transfer, and recombination processes of the photogenerated
electron-hole pairs in the semiconductor particles [22]. Fig. 8
shows the PL spectra with 325 nm excitation wavelength in the
the photocatalysts surface. A literature survey indicates that IR
range of 400–600 nm for P25, SVO, and SVO loaded compos-
spectroscopic studies of ammonia adsorbed on solid surfaces
ites at room temperature. The PL intensity of these samples
have made it possible to distinguish between Brønsted and Lewis
decreases in the order of P25 > SVO > 17SVO/SBA-15 > 60SVO/SBA-
acid sites of a catalyst [16–21]. Before the DRIFT measurements,
15 > 70SVO/SBA-15 > 34SVO/SBA-15 > 51SVO/SBA-15. The PL of
the samples were saturated with NH3 /N2 , flushed with N2 flow
SVO/SBA-15 samples show obvious decrease in the intensity of PL
to remove physically adsorbed ammonia, and then heated from
spectra as compared to SVO, indicating the recombination of pho-
303 K to 523 K. The intensity of chemisorption was determined
toelectrons and holes is efficiently suppressed in the composite
based on the irreversible adsorption of ammonia. Fig. 7 shows
semiconductors. The intensity of photoluminescence spectra cor-
the IR spectra of ammonia adsorbed onto SVO and SVO/SBA-15
responds to the recombination rates of the holes formed in the O2p
samples which were heated at 523 K for 30 min. The existence
band and the electron in the V3d band. The slower recombination
of NH4 + ions adsorbed onto Brønsted acid sites of the silver
process of photogenerated charges (the less the PL intensity) can
facilitate the enhancement of photocatalytic activity of SVO/SBA-15
composite.
3.6. DRIFTS study for recyclability of photocatalyst
During the photocatalytic reaction, organic pollutants are
supposed to be adsorbed or concentrated in situ and then photo-
degraded in vitro under factory process; therefore, it is important
to evaluate the catalyst recyclability in situ. Since 51SVO/SBA-
15 had the highest apparent rate constant, it was chosen for the
recyclability test. A complete cycle was composed of adsorption
under darkness for 30 min and then an illumination reaction for
60 min. After the 1st cycle, the catalyst was regenerated in situ
by further irradiating the LED light for 1 h. Then, the catalyst was
reused in situ without any washing or thermal treatment for the
2nd cycle. The reliability test was stopped when the catalyst was
deactivated as ascertained from DRIFTS and color analyses. The cat-
alyst reliability results were expressed as IR spectra. The results
Fig. 7. IR spectra of NH3 adsorbed onto SVO and SVO/SBA-15 samples at 523 K. of P25 and 51SVO/SBA-15 are shown in Fig. 9. After exposing P25

7. 230 W.-S. Chang et al. / Applied Catalysis A: General 407 (2011) 224–230
4. Conclusion
Environmentally friendly SVO/SBA-15 photocatalysts were
synthesized using hydrothermal synthesis without a high-
temperature calcination process. XRD and HRTEM results indicate
that SVO/SBA-15 composites had three kinds of phase and that SVO
dispersed well in the channels or on the surface of SBA-15 without
affecting the SBA-15 mesoporous structure, respectively. The mass
spectra indicate that the main oxidation product of toluene is ben-
zaldehyde, which is strongly adsorbed on the surface of the catalyst.
The SVO/SBA-15 photocatalyst has a much higher photodegrada-
tion ability for toluene than does P25. Based on the recyclability test,
the accumulation of benzaldehyde on the P25 surface appears to be
responsible for its deactivation; no deactivation was observed for
51SVO/SBA-15, which was still stable after 2nd cycle as evidenced
by DRIFTS analysis. The existence of the acidity of the SVO/SBA-15
composites was confirmed using DRIFTS. A bicrystalline framework
of ␣-Ag3 VO4 and Ag4 V2 O7 and high intensities of Brønsted and
Lewis acids are responsible for the enhanced adsorption capac-
ity, superior photoactivity, and long term stability of SVO/SBA-15
composites.
Acknowledgements
The authors are grateful to the National Science Council of
Taiwan (grant no. NSC 98-2221-E-168-008) and the Bureau of
Energy, Ministry of Economic Affairs (grant no. 7455VH7200), for
supporting this study.
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