Applied Surface Science 378 (2016) 473–478

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Applied Surface Science

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / a p s u s c

EnhancedphotocatalyticactivityofsupportedTiO2 byselective surface

modificationofzeoliteY
Kiros Guesha,b, Carlos Márquez-Álvarezc, Yonas Chebudea, Isabel Díaza,c,∗

a
Chemistry-Department, Addis Ababa University, P.O. Box 1176, Addis Ababa, Ethiopia b Mizan-Tepi
University, P.O. Box 260, Mizan-Teferi, Ethiopia
c
Instituto de Catálisis y Petroleoquímica, CSIC, c/Marie Curie 2, 28049 Madrid, Spain

article info abstract

Article history: Zeolite Y was treated using ammonium acetate and ammonium fluoride sequentially. As a consequence the aluminum from the surface
Received 25 January 2016 was selectively removed. Then, loading with TiO2 (20 wt%) led to a final photocatalyst. The samples were characterized by X-ray
Received in revised form 4 April 2016
diffraction (XRD), elemental analysis (ICP-OES), N2 adsorption, diffuse reflectance UV–vis spectroscopy (DRS),
Accepted 5 April 2016 Available
photoluminescence spectroscopy (PL), and X-ray photoelectron spectroscopy (XPS). It was found that 50% of the Al atoms were
online 7 April 2016
removed from the surface of the zeolite without affecting the framework structure. The TiO2/treated zeolite sample yielded 92%
photocatalytic degradation of 10 ppm methyl orange (MO), a model pollutant, while the TiO2/parent zeolite converted only 7.6%. The
Keywords:
mass normalized turnover rate (TORm) of the treated zeolite loaded with TiO2 was about 12 times higher than that of the parent zeolite
Photocatalysis
loaded with the same amount of TiO2 precursor. This higher photocatalytic activity of the TiO2 supported on treated zeolite can be
Zeolite
Titanium oxide
attributed to a more efficient interaction of the TiO2 with the zeolite leading to higher adsorption capacity. Reusability of the
Methyl orange photocatalysts was assessed by performing three consecutive reaction cycles that showed no significant loss of photocatalytic activity.
Dealumination © 2016 Elsevier B.V. All rights reserved.

1. Introduction Curie 2, 28049 Madrid, Spain.

E-mail address: [email protected] (I. Díaz).
It has been widely reported that photocatalysis is a
http://dx.doi.org/10.1016/j.apsusc.2016.04.029 0169-4332/© 2016
promising technology in textile wastewater treatment. Elsevier B.V. All rights reserved.
Among the many tested photocatalysts, TiO2 is found to be nanoparticles due to their photochemical stability, transparency
superb owing to its relatively high photocatalytic activity, to UV–visible radiation above 240 nm wavelength, unique
suitable band position, reasonable price and photo stability structures, uniform pores and channels, large specific surface
[1,2]. However, TiO2 has apparent challenges in its practical area and tunable hydrophilic/hydrophobic properties [4,6,12–
use, such as the difficulties in recycling (recovering) [3–5] 16]. Different authors reported enhanced photocatalytic
and pre-concentrating target molecules (low adsorption activity of TiO2 supported on zeolites compared to its
capacity) [4–7] and high aggregation tendency, which unsupported pristine counterpart [17–28]. However, zeolites
restrict the usage of TiO2 nanoparticles. In addition, the fate also cause access limitations and mass transport difficulties
of nanoparticles in general and TiO2 in particular when [29,30]. Different top-down treatment strategies such as acid,
released to the environment has not been well studied. steam, and base treatment are applied at industrial scale to tune
Recently, research reports are indicating the toxicity of the chemistry of zeolites for pre-designed applications [29,30].
nanosized TiO2 [8–11]. Therefore, TiO2 has to be supported However, such treatments lead to some amorphization of the
(immobilized) on other materials to enhance adsorption, framework that frequently plays against the catalyst efficiency.
maintain reusability, prevent aggregation and avoid Therefore, mild treatment conditions should be pursued to tune
leaching of toxic nanoparticles. Among the various the surface chemistry of zeolites without severely affecting the
substrates, zeolites are suitable candidates for supporting zeolite framework structure.
TiO2 In our previous work [31] we tested mild treatments on
mordenite zeolite. These treatments are based on the commonly
employed cation exchange procedures, which eventually upon
calcination generate certain degree of mesoporosity [32]. The
∗ Corresponding author at: Instituto de Catálisis y Petroleoquímica, CSIC, c/Marie
choice of NH4Ac solutions is based on its mild pH (6) and the
474 K. Guesh et al. / Applied Surface Science 378 (2016) 473–478
chelating effect of acetate. The moderate acidity together with
the presence of chelating agents is expected to dealuminate TiO2
selectively surface Al atoms [29]. The aim of the subsequent
treatment by NH4F solution is to dissolve the extra framework Si
species. On the other hand, we have found that zeolite Y (Zeolyst sity (a.u) 20TZY-5t
CBV 400) is photocatalytically inactive upon loading of TiO2,
while zeolite USY (Zeolyst CBV 760) was active despite having 20TZY-5
the same zeolite framework structure [33]. Similar to our
en
previous report, Jansson et al. have also reported the poor Int
activity of TiO2 supported on a similar zeolite Y (CBV 600) in the
photocatalytic conversion of formaldehyde [17]. Thus, herein
ZY-5t
we report how the treatment of Zeolite Y (CBV 400, SiO2/Al2O3
= 5.2) using ammonium acetate (NH4Ac) and ammonium
fluoride (NH4F) enhances the photocatalytic activity of
supported TiO2. The samples were characterized using XRD, N2 ZY-5
adsorption/desorption isotherms, ICP-OES, UV–vis-DRS, PL 10 20 30 40 50 60
and XPS. Finally, the photocatalytic activity was tested in the
ο
degradation of a model textile azo dye, methyl orange (MO). 2θ ( )
Reusability of the photocatalyst was tested and, after the
Fig. 1. XRD profile of ZY-5, 20TZY-5, 20TZY-5t and TiO2.
reaction, the treated water was analyzed for Ti species to
evaluate leaching during the photocatalytic reaction.
2.2. Characterization ofthe photocatalyst

2. Experimental X-ray diffraction (XRD) patterns were collected with a

PANalytical XıPert´ Pro diffractometer (CuK radiation =
2.1. Preparation ofphotocatalyst 0.15406 nm). Nitrogen adsorption and desorption isotherms
were measured in a Micromeritics ASAP 2420
Commercially available zeolite CBV 400 SiO2/Al2O3 = 5.2 physisorption analyzer and all the samples were degassed at
was purchased from Zeolyst. Hereafter, this sample is referred to 350◦C for 16 h prior to data collection. Chemical composition
as ZY-5. Parent zeolite ZY-5 was treated as follows [31]: 8 g of was determined by Inductively Coupled Plasma Optical
zeolite were stirred in 104 mL of 3 M CH3COONH4 (NH4Ac) Emission Spectrometry (ICP-OES) using a PerkinElmer
solution at room temperature for 30 min. Then 48 mL of 2.4 M Optima 3300 DV equipment. Digestion of the samples was
NH4F solution was added drop wise under stirring. The carried out by alkaline fusion. UV–vis Diffuse Reflectance
suspension was stirred for 30 min at 80◦C. The sample was then Spectroscopy (DRS) measurements were done using a
filtered and washed with distilled water, dried at 100◦C for 12 h Varian Cary 5000 double-beam UV–vis-NIR
and calcined at 550◦C for 6 h. The sample was labeled ZY-5t to spectrophotometer. Collected spectra were converted to
indicate ZY-5 treated. For the loading of 20 wt% TiO2 on ZY-5, Kubelka–Munk function, F(R) versus wavelength.
4.48 g of ZY-5 was added to a solution of 5.68 mL of titanium (IV) Photoluminescence spectra were recorded using a
butoxide Ti(OC4H9)4 in 11.2 mL of deionized water and 56.8 mL PerkinElmer LS 50B Luminescence Spectrometer equipped
of 2-propanol. The mixture was kept under stirring at room with a Xe lamp source. The measurement was done at room
temperature for 24 h. The solvent was removed by rotary temperature with excitation wavelength at 310 nm and the
evaporator. It was then dried at 110◦C and calcined in air at 400◦C same sample size was taken in all measurements. The surface
for 3 h. Similar procedure was followed for TiO2 loading on ZY- chemical composition was analyzed by X-ray photoelectron
5t. For comparison purposes, TiO2 was also synthesized by a spectroscopy (XPS) using a SPECS instrument with UHV
similar method without adding zeolite. The samples were then system (pressure of about 10−10 mbar), equipped with a
labeled 20TZY-5, 20TZY-5t and TiO2 for the 20 wt% TiO2 PHOIBOS 150 9MCD energy analyzer.
loaded on parent zeolite, 20 wt% loaded on treated zeolite and
pristine TiO2, respectively. A non-monochromatic Mg X-ray source was used working at
200 W and 12 kV. The powder samples were pressed into self-
supporting wafers and stuck on the sample holder with
double-sided adhesive conductive carbon tape. Spectra were
referenced against the C 1s emission line of adventitious
carbon (binding energy set to 285.0 eV) to correct for
charging effect. Relative atom ratios were calculated from
the sum area of the two 2p level components of Ti, Si and Al,
using the relative sensitivity factors provided by Casa XPS
software.

2.3. Photocatalytic test

For a particular photocatalytic test, 0.5 g of sample was

suspended in 750 mL of a 10 ppm aqueous solution of methyl
orange (MO) in a quartz glass reactor equipped with quartz Fig. 2. N2 adsorption desorption isotherms of ZY-5, 20TZY-5, 20TZY-5t
isotherms have been vertically shifted for clarity.
glass cooling pipe and ports for sample withdrawing and
oxygen purging. The mixture was stirred for 30 min in
continuous purging of air to maintain adsorption-desorption
equilibrium of MO on the powder photocatalyst material. 3. Results and discussion
Then, the suspension was irradiated with a 150W UV lamp
(Heraeus medium pressure mercury lamp) and samples 3.1. Photocatalyst characterization
were withdrawn in time intervals for analysis after filtering
out the photocatalyst. The withdrawn samples were analyzed X-ray diffraction profiles of ZY-5, ZY-5t, 20TZY-5,
with a PerkinElmer Lambda 950 UV–vis 20TZY-5t as well as pure TiO2 are shown in Fig. 1. According
spectrophotometer. The spectrum of the sample was to the diffraction patterns, the crystalline framework of the
recorded from 800 to 200 nm and the absorbance at max was zeolite has been maintained and the crystallinity has
taken for concentration calculation. For the reusability test, increased after the mild modification treatment. The zeolite
the photocatalyst was recovered after the degradation crystalline framework of both the ZY-5 and ZY-5t zeolite is
reaction was completed, then washed with water and dried at also maintained after the 20% wt TiO2 loading. However, the
110◦C. The second and third cycles were conducted as intensities of the zeolite diffraction peaks decreased. For
described above. After the photocatalytic reaction, the pristine TiO2 calcined at 400◦C, the diffraction peaks at
leaching of Ti species in the treated water was measured by and
ICP-MS. The analysis was done with a PerkinElmer 54.5◦ (105) can be assigned to the anatase phase, and
NexION 300X ICP-MS equipment provided with collision diffraction peaks at 2theta = 27.6◦ (110), 36.1◦ (101), 41.3◦
gas technology, with RF power of 1500 W, auxiliary gas (H2) and 56.7◦ are assigned to rutile. The most intense peaks of the
flow 1.2 L/min, nebulizer gas (Ar) flow 0.90 L/min and anatase phase (25.4◦, 48.0◦ and 54.5◦) can also be identified in
plasma gas coolant (Ar) flow 18.0 L/min. External the pattern of sample 20TZY-5t, overlapping with the zeolite
calibration graph was constructed using a series of aqueous reflections. However, no detectable intensities for the rutile
titanium standards at concentrations 0.0, 0.5, 1.0, 5.0, 10 phase can be observed, indicating that somehow the
and 20ppb. Titanium isotopes (47Ti presence of zeolite delays the phase transition of anatase to
the most stable phase of TiO2, rutile. Since the intensities at
27.6◦ overlapped with the diffraction pattern of the zeolite,
and 49Ti) were monitored in sample solutions that were
the intensity at 36.1◦ (101) was used to ascertain if there is
diluted
detectable rutile phase of TiO2. In the case of sample 20TZY-
5, peaks corresponding to any TiO2 phase can hardly be
10-fold using 1% nitric acid solution before measurement. observed in the XRD pattern. This suggests that this sample
Concentrations evaluated for both isotopes of Ti agreed well possesses nanocrystalline TiO2 with a particle size below the
showing absence of polyatomic interference in the results of detection limit of the technique, which indicates a much
analysis. The measurements were done with three replicates higher dispersion of the TiO2 phase on the parent zeolite
per sample.
K. Guesh et al. / Applied Surface Science 378 (2016) 473–478 475

analysis collected in Table 2, it can be deduced the Si/Al ratio of ZY-5 increased upon
treatment. The Si/Al ratio ofZY-5 was
0.0 0.2 0.4 0.6

1.0 compared to the dealuminated one.

Relative pressure The N2 isotherms of ZY-5, ZY-5t, 20TZY-5 and 20TZY-
5t are plotted in Fig. 2. The mild modification treatment did
476 K. Guesh et al. / Applied Surface Science 378 (2016) 473–478
not infer noticeable changes in the textural properties of the 3.2. Photocatalytic activity
Zeolite Y, only small variation in the shape of the isotherms
can be observed at high relative pressure probably due to Photocatalytic degradation of MO on the loaded zeolites
external modifications. Table 1 collects the surface area (both before and after treatment) and pure TiO2 is plotted versus
values which reflect that only the external surface varies time in Fig. 5. As it can be seen from the plot, the photocatalytic
upon treatment. TiO2 exhibited type IV isotherm, which is degradation of MO on 20TZY-5 (7.6%) is way below the
related to the textural porosity mainly between TiO2 photocatalytic activity of pristine TiO2, which renders about
particles. The loaded zeolites exhibited a mixture of type I 58%degradation in
and IV isotherms proving that the microporosity of the
zeolitic structure was retained even after the loading. TiO2
loading decreased the surface area (SBET) as it can be seen
from the data collected in Table 1. This indicates that some of
the pores of the zeolite are either blocked and/or populated
with TiO2 particles. From the ICP 20TZY-5 and 20TZY-5t
were collected. Original and fitted spectra in the regions
corresponding to Ti 2p, Si 2p and Al 2p levels are shown in
Fig. 3. Since Si and Al 2p1/2 and 2p3/2 cannot be resolved due
to strong overlapping, these spectra have been simulated
using a single peak. The binding energy (BE) values
obtained are typical of Ti(IV), Si(IV) and Al(III) oxides. For
both samples, the BE determined for Si 2p and Al 2p are the
same within the experimental error. However, a slight
difference is obtained for Ti 2p (0.5 eV) which might indicate
some difference in the TiO2 phase that might be attributed to
the difference in chemical composition of the surface of
zeolite crystals (may be causing different TiO2 dispersion or
different chemical interaction with the zeolite surface).
Quantitative surface chemical analysis is presented in Table
2. The surface Si/Al ratio calculated for the loaded parent
zeolite (2.9) is very close to the bulk composition (2.6).
Treatment of zeolite ZY-5 with ammonium acetate removes
Al from the surface, increasing the surface Si/Al ratio to 5.8
(this means that 50% of the Al on the outer part of the zeolite
crystals is removed). The higher Si/Al ratio determined by
XPS compared to the bulk Si/Al ratio confirms that
dealumination occurs preferentially in the outer region of
the zeolite crystals. XPS analysis also shows that there is a
difference in the concentration of Ti on the surface of both
zeolites. Although the same amount ofTiO2
(ca. 20 wt%) was loaded on both the parent and treated zeolites,
the XPS results indicate that higher amount of TiO2 is present on
the outer region of the particles of the treated zeolite compared to
the parent zeolite. This conclusion is in agreement with XRD
data that suggest a higher dispersion of the TiO2 phase on the
parent zeolite.
Diffuse reflectance UV–vis spectra of pure zeolites, loaded
zeolites and pristine TiO2 are shown in Fig. 4. From these spectra,
it can be seen that the pure zeolites do not show any absorbance
above 240 nm wavelength. Upon loading 20% of TiO2 to both
parent and treated zeolites, the absorbance edge of the materials
is extended. The absorbance edge of the loaded zeolites showed
blue shift as compared with the absorbance of pure TiO2 [34,35].
In Fig. 4, the absorption band at around 200–240 nm is due to
electron transfer excitation from the ligand-oxygen to an
unoccupied orbital of the Ti4+ framework. The loaded zeolites
spectra are also characterized
by a large unresolved absorption band
ranging from 375 to 240 nm, which is assigned to the electronic
transition from 2p(O) to 3d(Ti), corresponding to the valence
band to the conduction band transition according to the energy
band structure of TiO2 [36–40], while it appears from 412 to 240
nm for the pristine TiO2.
Table 2
Atomic ratios from the bulk and surface analyses.
Sample ICP-OES Bulk analysis XPS surface analysis

Tiwt% Si/Alat. ratio Ti/(Si + Al)at. ratio Si/Alat. ratio Ti/(Si + Al)at. ratio

Fig. 3. Si 2p, Al 2p and Ti 2p core-level spectra of samples 20TZY-5 (A) and20TZY-5t(B).

ZY-5
20TZY-5
20TZY-5t
TiO2
F(R)

200 300 400 500

Wavelength (nm)
12 times higher than for its counterpart 20TZY-5 and 9.5 times
Fig. 4. Diffuse UV–vis absorbance spectra of ZY-5, 20TZY-5, 20TZY-5t and
higher than that ofthe pristine TiO2.
TiO2.

Fig. 5. MO Photocatalytic degradation. The dashed line indicates the starting of

UV irradiation.
90 min under UV light irradiation, in agreement with our
previous report [33]. In contrast, 20TZY-5t reaches 92%
degradation of MO in 90 min. The increased photocatalytic Jansson et al. (2015) calculated the mass normalized
degradation activity of the TiO2/treated-zeolite system when photocatalytic conversion of HCHO to HCOOH and found a
compared to pristine TiO2 is even more pronounced if the rate of 13.5 times higher photocatalytic conversion for TiO2
the photocatalytic degradation is normalized by mass of the supported on ZSM-5 (Si/Al = 23) than for the unsupported
photoactive material, TiO2. Although common understanding TiO2. Furthermore, the authors reported that the enhanced
is yet to be reached in the literature for calculating turnovers of photocatalytic activity is obtained from the supporting
different photocatalysts, mass normalized turnover rate (TORm: zeolites with higher Si/Al ratio which is similar to our result
moles converted of MO per gram of photocatalyst per unit time) since the Si/Al ratio of 20TZY-5t is higher than that of 20TZY-
has been used in some literature [41,42]. From the data collected 5 [17]. Kuwahara et al. (2011) also reported similar trend of
in Table 2, it can be observed that the TORm of 20TZY-5t is about
478 K. Guesh et al. / Applied Surface Science 378 (2016) 473–478
increasing photocatalytic activity as the Si/Al ratio of the photocatalytic degradation reaction directly and/or
supporting zeolite increases [28]. indirectly. Furthermore, a possible reason for the
A photocatalyst recycling study was conducted to enhancement of the photocatalytic activity in 20TZY-5t
determine the stability of the synthesized material over three could also be related to a low recombination rate of the
cycles. At the end of the first photocatalytic cycle, the photogenerated electron/hole pairs. Photoluminescence
photocatalyst was separated spectra helped us to trace the fates of the photogenerated
K. Guesh et al. / Applied Surface Science 378 (2016) 473–478 477

Time (min) electron/hole pairs (Fig. 7). For effective photocatalytic

reaction the photogenerated electron/hole pair should not
Fig. 6. Reusability test of 20TZY-5t.. The dashed line indicates the starting of recombine. The photoluminescence (PL) spectra could be
UV irradiation.
taken as comparison parameter since the same amount of
sample was taken and measured in the same condition. In
Fig. 7, emission bands of the samples at around 371–373.5
from the resulting suspension, washed with deionized water,
nm can be observed. These emission bands are mainly due to
oven dried at 110◦C, and reused. The same procedure was
band to band recombination (con-
employed in all cycles used. As shown in Fig. 6, the
photocatalytic activity did not vary significantly in the 3 20TZY-5t
cycles tested. The small decrease in the degradation 20TZY-5
percentage is probably due to the accumulation of organic
intermediates in the cavities and/or on the surface of the
photocatalyst, affecting the adsorption of MO and reducing
the photocatalytic activity of the material in the subsequent .u)
run. a(
In this particular work, the adsorption capacity of the ty
ensi
modified zeolite, 20TZY-5t, was found to be higher than that
of the pristine system, 20TZY-5. It was found that after 30 Int
min stirring in the dark, 20TZY-5t adsorbed about 26.5% of
the total amount of MO in solution, whereas only 0.01% of
MO was adsorbed on 20TZY-5. Thus, it can be concluded
that 20TZY-5 shows no photoactivity due to its lack of MO
adsorption. The higher adsorption capacity in 20TZY5t may
be due to the higher hydrophobicity of the zeolite surface
since 50% Al is removed from its surface after the mild
treatment. Moreover, this increased hydrophobicity might 340 350 360 370 380 390 400 410
also be the reason behind the different Ti content on the Wavelength (nm)
surface (the XPS data indicate that the Ti/(Si + Al) ratio on the
surface of 20TZY-5 is much lower, almost by 50%, than that
of 20TZY-5t) though both have similar Ti/(Si + Al) ratio in Fig. 7. PL spectra of 20TZY-5 and 20TZY-5t.
the bulk according to ICP-OES analysis. This efficient
adsorption of active species is reflected in the electronic
duction band to valence band recombination emissions) [43,44].
properties. As it can be observed in Fig. 4, UV–vis absorption
These spectra show that the PL emission intensity of 20TZY-5t is
band area of the 20TZY-5t is higher than that of 20TZY-5,
lower than that of 20TZY-5 indicating that there is a lower rate of
being this parameter comparable given that the same amount
band to band recombination of photogenerated electron/hole
ofsample was taken for the measurement and the two samples
pairs, which could also be a reason for the higher photocatalytic
contain similar amount of TiO2 in the bulk analysis. The
activity of 20TZY-5t.
higher absorption coefficient indicates the absorbance of
Although it is reported that TiO2 in the bulk state is not toxic,
large number of photons which in turn produces large
recent reports are indicating its toxicity in its nano sized regime.
number of electron/hole pairs which are responsible for the
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