Colloids and Surfaces A: Physicochem. Eng.

Aspects 513 (2017) 2027

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Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

ZnO supported on zeolites: Photocatalyst design, microporosity and

properties
Vagner Roberto Batistela a , Leonardo Zavilenski Fogaca a , Silvia Luciana Fvaro b ,
Wilker Caetano c , Ndia Regina Camargo Fernandes-Machado d , Noboru Hioka c,
a
Departamento de Tecnologia, Campus de Umuarama, Universidade Estadual de Maring, Av. Dr. ngelo Moreira da Fonseca, 1800, CEP 87506-370
Umuarama, Paran, Brasil
b
Departamento de Engenharia Mecnica, Universidade Estadual de Maring, Av. Colombo, 5790 Jardim Universitrio, Maring, Paran CEP 87020-900,
Brasil
c
Departamento de Qumica, Universidade Estadual de Maring, Av. Colombo, 5790 Jardim Universitrio, Maring, Paran CEP 87020-900, Brasil
d
Departamento de Engenharia Qumica, Universidade Estadual de Maring, Av. Colombo, 5790 Jardim Universitario, Maring, Paran CEP 87020-900,
Brasil

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

Three ZnO catalysts supported on

zeolites were synthesized by the
humid impregnation method.
In the larger pore size of zeolites, ZnO
was included into the micropores.
BET analysis indicates reduction of
specic surface area.
ZnO formed needle-shaped crystal-
lites on NaA zeolite.
Bandgap values of the catalysts in
NaA and NaY are close to the pure
ZnO.

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

Article history: ZnO was supported in three different zeolites aiming at new photocatalysts. In the zeolite NaA, the crys-
Received 14 August 2016 tallization of ZnO was on the external surface while for zeolites NaY and USY it occurred predominantly
Received in revised form 1 November 2016 inside the micropores, as indicated by XRD diffractograms and by transmission electron microscopy. The
Accepted 8 November 2016
bandgap and the zero point of charge indicated that the increase in ZnO content approaches these param-
Available online 9 November 2016
eters to values of pure oxide. In the catalysts supported on USY, signicant changes were not observed
in the bandgap values due to the incorporation of ZnO in their micropores. Therefore, each synthesized
Keywords:
catalyst has potential applications in heterogeneous photocatalysis.
Photocatalysts
Zinc oxide 2016 Elsevier B.V. All rights reserved.
Zeolites
Porosity

Corresponding author.
E-mail addresses: vagner.batistela@yahoo.com.br (V.R. Batistela), lzfogaca@gmail.com (L.Z. Fogaca), slfavaro@uem.br (S.L. Fvaro), wcaetano@uem.br (W. Caetano),
nrcfmachado@uem.br (N.R.C. Fernandes-Machado), nhioka@uem.br (N. Hioka).
http://dx.doi.org/10.1016/j.colsurfa.2016.11.023
0927-7757/ 2016 Elsevier B.V. All rights reserved.
 V.R. Batistela et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 513 (2017) 2027
1. Introduction
Zinc oxide (ZnO) is a very common chemical, and also a useful
and low-cost material [1,2] that is traditionally used as a pharma-
ceutical component [3,4], a pigment [5] and an activator of rubber
vulcanization [6]. New applications involve its use in solar cells [7],
gas sensors [810] and in light-emitting diodes (LED) fabrication
[11,12].
Additionally, ZnO is one of the most promising materials for
the development of new environmental technologies. The semi-
conductor properties make this oxide a catalyst for degradation
of several recalcitrant substances by using heterogeneous photo-
catalysis [1,1318]. When this semiconductor absorbs ultraviolet
or visible radiation, it promotes the formation of highly oxidiz-
ing species that destroy chemicals, such as organic pollutants. The
mechanism of this process involves adsorption of the substrate on
the catalyst surface, which is highly dependent on parameters such
as pH, temperature, catalyst stability, area and substrate concentra-
tion, among others [1923].
The ZnO exhibits bandgap of 3.2 eV, whose value is similar to
TiO2 , the most important photocatalyst. ZnO is described to show
high efciency, so that its low cost is suitable for industrial appli-
cations. On the other hand, ZnO efciency is limited due to its
low adsorption capability (small active area) and the possibility of
photo-corrosion [14,24,25].
In this sense, catalysts design can help the understanding of the
adsorption and photo-activity of these materials. These parameters
depend on the preparation method of ZnO, which can be produced
in several morphologies and sizes, especially in nanoscale dimen-
sions [26,27]. Although the use of tiny ZnO particles with broad
surface area can improve their photo-activity, nanoparticles of ZnO
are not easy to recover at the end of the processes. To solve this
problem, one interesting alternative is the ZnO being supported
on inert or active materials that also improve their adsorption
properties and, consequently, the catalyst efciency, showing easy
recovery by simple ltration or deposition [2832].
Hybrid catalysts formed by ZnO impregnated on zeolites is a
strategy that combines the solutions previously pointed out. They
can show broad specic area, high amount of hydrophobic and
hydrophilic active sites and adequate crystallinity/geometry. For
these purposes, synthetic or natural zeolites obtained by precip-
itation or humid impregnation can be utilized [2934]. For the
impregnation of the TiO2 in zeolites, several investigations have
been carried out with good results in photocatalysis [3542],
especially with the improvement of the photocatalysis efciency
compared to bulk catalyst.
Several articles have reported the characteristics of ZnO sup-
ported on zeolites, such as zeolites ZSM-5 [4345], Y [43,4649],
X [33,5052] and A [53], among others [29,54,55]. However, these
studies were individualized without a comparison among differ-
ent zeolites, which was done in the present work. Therefore, this
paper shows a general description and the development of ZnO sup-
ported on three zeolites for applications on photocatalysis. First of
all, we describe a simple synthetic route for preparation of catalysts
by humid impregnation in three different zeolites, sodic forms:
zeolite Y (NaY), zeolite A (NaA) and zeolite Y ultrastable (USY).
Secondly, structural properties of these materials are determined.
Finally, some important parameters for heterogeneous catalysis are
discussed.
2. Materials and methods
2.1. Materials
The solid matrix zeolites used were the commercial A (Oxanyl)
and Y (Fbrica de Catalisadores Carioca) zeolites. In addition, USY
was synthesized by our research group, as already reported [56].
21
The zeolites A and Y have sodium as the compensation cation.
Therefore, they were named as NaA and NaY, respectively. Both
cations, Na+ and H+ , were present in the zeolite USY, so it was
named simply as USY. The impregnated catalysts were obtained
with Zn(NO3 )2 6H2 O (Synth) as a starting precursor. All experi-
ments made use of deionized water.
2.2. Catalyst synthesis
The Zn(NO3 )2 6H2 O was dried in a vacuum desiccator for 24 h
and the zeolites were dried at 110 C for 2 h. An adequate amount of
reactants was mixed in 50 mL of acidied water with three drops of
glacial acetic acid in a borosilicate glass ask, targeting 5% and 10%
of ZnO in the impregnated catalysts. Under continuous agitation
using a magnetic stirrer for 20 min, the mixture was heated at 80 C
until water evaporation was complete. The drying was nalized at
100 C for 12 h, followed by calcination at 500 C for 5 h. After that,
the dried material was sieved with a 125 m mesh in order to obtain
small uniform particles.
2.3. Catalyst characterization
The zinc content was determined by Flame Atomic Absorption
Spectroscopy (FAAS) with 200 mg of each solid sample digested
and pre-concentrated in a TeonTM ask with 0.5 mL of aqua regia
(HNO3 :HCl, 1:3) and 3.0 mL of concentrated uoride acid until
liquid reduction up to 0.5 mL. The mixture was cooled and then
10.0 mL of deionized water, 5.0 mL of H3 BO3 at 4% and 1.0 mL of
concentrated HCl were added, and heated again until it became
transparent. After that, the solution was cooled and diluted to a con-
centration around 2.0 ppm of Zn. The absorbance measurement was
performed in a VARIAN SpectrAA atomic absorption spectropho-
tometer model 50 B at 213.9 nm (standard zinc emission in the
analyzed concentration range). Even with this experimental conr-
mation of ZnO percentages, the catalysts were named by expressing
the theoretical percentage of ZnO in the zeolitic support. Thus, for
example, 5NaA catalyst is the one synthesized aiming at theoreti-
cally 5% of ZnO on zeolite A.
XRD measurements of the catalysts were done by using a Bruker
D8 Advance diffractometer with the radiation source for cupper
(CuK, 40 kV and 50 mA). The diffractograms were interpreted with
the JCPDS database of the Philips Xpert software.
The adsorption-desorption isotherm of N2 was performed with
a Quantachrome 1200 apparatus. For the analysis of the curves we
utilized BET method (p/p0 from 0.05 to 0.35) for specic area, t-plot
method for external area, volume and area of micropores; and BJH
method for diameter determination of the mesopores.
Images of Transmission Electronic Microscopy (TEM) were
obtained by a JEOLJEM-1400 instrument operated at 120 kV.
Photoacoustic Spectra were obtained in the UV and Visi-
ble region by an Oriel Corporation 68820 xenon arc lamp of
1000 W. The radiation was modulated by an Oriel Instruments
77250 monochromator, lters and nally by the Stanford Research
Systems SR540 mechanical modulator at a frequency of 25 Hz.
The non-radiative radiation was measured with a high sensitive
Bruel&Kjaer model 2639 microphone, with 12 mm of diameter and
a synchronic amplier lock-in EG&G 5110. The bandgap values
were determined from the photoacoustic spectra [57] employing
Eq. (1) [5860]:
h = A0 (h Eg )2 (1)
where: is the absorption coefcient; h and Eg are, respectively,
the photon energy and the bandgap energy, both in eV. A0 and 2
are constants that depend on the electronic transition type.
22 V.R. Batistela et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 513 (2017) 2027
Table 1
Percentage of ZnO impregnated in different zeolites.
5% ZnO 10% ZnO
NaA 5.80 12.25
NaY 6.50 13.21
USY 5.73 12.92
Zero point of charge values (ZPC) were obtained according to
KENG and UEHARAs (1974) method [61]. ZPC values were calcu-
lated by Eq. (2).
ZPC = 2 pHKCl pHaq
where pHKCl is the pH of KCl solution of 1.00 mol/L and pHaq is the
pH of the aqueous solution, both samples obtained after ltration
of solid catalyst. The pH of the ltrated solution was measured by
using a QUIMIS Q-400MT pHmeter.
3. Results and discussion
The description of the composition, structure and morphology of
the materials is an important reference for predicting their behavior
as catalysts.
3.1. Composition
The zinc content in the catalyst with the sample digestion and
the release of zinc in free form was determined by FAAS at 213.9 nm,
which is very sensitive in the concentration range evaluated. The
found percentages of ZnO impregnated in the zeolitic supports are
shown in Table 1.
The zinc oxide content in the catalysts is actually 6% and 13%
(Table 1). Probably, the variation in relation to the planned values
(5% and 10%) can be justied: (i) some water content in zeolites
before the synthesis procedure; (ii) loss of water molecules from
zinc nitrate hexahydrate or (iii) some Zn2+ content adsorbed in zeo-
lites instead of ZnO. These factors maximize the weight proportion
of zinc oxide relative to weight of zeolite, raising the percentage of
ZnO.
3.2. X-ray diffractograms
In order to assess the structure of the synthesized catalyst,
diffraction patterns of the ZnO and the supported zeolites were
obtained. As shown in Fig. 1, ZnO presents three important 2
diffraction signals: 31.8 , 34.4 , and 36.2 , with a relative intensity
of 0.64, 0.36, and 1.00, which corresponds to wurtzite structure.
In the supported catalysts 5NaA and 10NaA, two signals of ZnO
in 31.8 and 36.2 appear. However, the 34.4 signal overlaps the
signal of the zeolite NaA (without ZnO), resulting in a broad peak
(Fig. 1). In the catalysts 5NaA and 10NaA there is the maintenance of
the material crystallinity after impregnation with the maintenance
of diffraction signs of the zeolite there is the maintenance of the
material crystallinity after impregnation and also the diffraction
signs of the zeolite, consequently.
In Fig. 2 the XRD patterns of NaY and USY catalysts have identical
signs that correspond to faujasite structure. The catalysts supported
on USY and NaY maintained the crystalline structure of zeolites and
no signal of ZnO was detected. It is suggested that this oxide can
occupy the pores of the zeolitic support, in small size of crystallites.
Unlike faujasite catalysts (NaY and USY), the presence of ZnO sig-
nals in the supported catalysts NaA (LTA structure) indicates that
this oxide is exposed in the outside of the support and the ZnO crys-
tallization occurred preferentially on the outside surface. The fact
that the pore size of faujasite zeolites (7.4 ) is higher compared
to the zeolite NaA (4.1 ) [62] allows for greater input of precursor
(2)
Fig. 1. XRD patterns of ZnO catalysts supported on NaA. The symbol represents
the ZnO signals.
solution into the pores of zeolite Y, so that the ZnO crystallization
occurs favorably in its inner region, generating small crystallites. In
the zeolite NaA, the smaller diameter cavity led to the crystalliza-
tion occurrence, not only in its inner region, but also on the external
surface, where larger ZnO crystallites were formed, which makes
it easier to detect. This result was reinforced by microscopies, as
shown later.
3.3. Textural analysis
Nitrogen adsorption-desorption isotherms of catalysts are rep-
resented in Fig. 3 curves described by the volume (V) of nitrogen
gas adsorbed-disadsorbed as a function of relative pressure (p/p0 ),
at 77 K.
In these curves, it is apparent that the process of adsorption-
desorption of N2 is reversible and without hysteresis. The shape of
the isotherms is type-I characteristics of microporous solids with
small external area [63]. The format of matching curves between
the supported catalysts and the pure zeolites indicates that the
zeolites texture remained after ZnO incorporation.
The BET method commonly presents limitations to the study
of materials with high microporosity caused by several reasons
[6468]: (i) reduced accessibility of nitrogen on the inner surface;
(ii) difculty to achieve chemical equilibrium within considerable
time; (iii) limitations in the description of monolayers multilay-
ers; (iv) unequal structure of each monolayer across the surface; (v)
difculty to locate the linear range of the BET plot; (vi) no possibility
of calculating the difference between heat of adsorption and lique-
faction of N2 due to the smaller diameter of the zeolite channels.
Despite all this, BET treatment is still used as a common method for
qualitative evaluation of textural parameters of catalysts [69].
In Table 2, BET areas of zeolites NaY and USY are very broad,
respectively, 646.6 m2 /g and 530.1 m2 /g. After ZnO impregnation,
the BET area decreases, as already described, by the incorporation
of this oxide to other zeolites: ZSM 5, NaY, beta [70] and nano-
clinoptilolite [29]. For the impregnation method, the specic area
of the supported catalyst decreased considerably. For instance, the
area of the catalysts 10NaY and 10USY decreased 35.4% and 51.2%.
Although these values are lower compared to the zeolites, they are
still quite large compared to pure ZnO values, only 20.0 m2 /g [71] or
25.5 m2 /g [72], varying according to the method of synthesis. The
important point is the large surface active area of ZnO impregnated
in zeolite, where ZnO is the real catalyst.
 V.R. Batistela et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 513 (2017) 2027 23

Fig. 2. XRD patterns of ZnO catalysts supported on NaY and USY.

Table 2
Textural analysis of ZnO catalysts supported on zeolites NaY and USY.

Specic Surface (m2 /g) CBET Smicro (m2 /g) Sext (m2 /g) Vmicro x 101 (cm3 /g) dporous (meso) ()

NaY 646.6 38.0 601.1 (100%) 45.5 3.2 (100%) 30.62

5NaY 554.3 27.2 509.8 (85%) 44.5 2.8 (87%) 30.60
10NaY 417.8 20.6 382.1 (64%) 35.7 2.3 (72%) 30.60
USY 530.1 29.9 464.5 (100%) 65.7 2.5 (100%) 30.72
5USY 426.7 40.6 368.9 (79%) 57.6 1.9 (76%) 30.70
10USY 258.5 33.8 223.6 (48%) 34.9 1.2 (48%) 30.60

240 larger cations, p. ex. calcium ion, as the hydration radius increases, it
cannot penetrate the pores and remains preferably on the external
NaY surface of the zeolite, increasing its area [76].
The catalytic action of zeolites for small molecules depends
200 5NaY
mainly on its microporosity. However, its effect on large molecules
USY
is more inuenced by the external area, since large molecules can-
not penetrate the micropores. Furthermore, for large molecules,
10NaY
V (cm /g)

160
secondary mesoporosity becomes important because it allows the
3

5USY diffusion and the transport of substrates. As shown in Table 2, there

was maintenance of mesopores diameter of about 30 , indicating
preservation after impregnation process.
120

10USY

80
0.0 0.2 0.4 0.6 0.8 1.0
3.4. Transmission electron microscopy
p/p0

Fig. 3. Nitrogen adsorption-desorption isotherms for ZnO catalysts supported on

zeolites NaY and USY .
In the study of zeolites, it is usually presented the specic areas
along with the constant C of the BET equation. Constant C should
be positive since the constant is related to the exponential capil-
lary condensation heat [73]. However, the values found for zeolites
show negative values caused by the high microporosity, which is a
method limitation that jeopardizes accurate determinations.
For zeolite NaA, the specic area was estimated as 11.2 m2 /g,
which is in agreement with the values of 9.2 m2 /g [74] and
11.2 m2 /g [75], determined by the same method. The lowest spe-
cic area of zeolite NaA is explained by the smaller volume of the
unit cell of the crystal structure LTA (1.870 3 ) in relation to the
faujasite (FAU) of NaY and USY (15.014 3 ) [62]. Moreover, the com-
pensation cation affects the pore opening, blocking it or keeping it
available. As the sodium ion has a small radius of hydration, it can
penetrate the pores of the zeolite, blocking them. In the presence of
Fig. 4 shows the micrographs of transmission electron
microscopy of the 10NaA catalyst. The material presented the tradi-
tional cubic zeolitic framework for zeolite A (Fig. 4a). On its surface,
as depicted in Fig. 4b, we can notice the presence of needle-shaped
crystallites attributed to ZnO formed from the impregnation. It is
estimated by Fig. 4b that the diameter of these small aggregates of
ZnO is at the range of 100200 nm.
Fig. 5a presents the micrographs of the catalyst 10NaY, which is
quite distinct from 10NaA. There were of ZnO distributed between
the inner and external parts of the zeolite. This result allied to XRD
and BET experiments pointed out that most of the ZnO is incor-
porated inside the zeolite Y cavity (the darker region), and a small
fraction of ZnO is present on the external surface. This morphology
is similar to those reported in the literature [46,77].
In Fig. 5b, the micrograph of the catalyst 10USY shows ZnO
formation inside the zeolite structure instead of external crystal-
lization. The larger area reduction and micropore volume (Table 2)
can be associated to penetration of the precursor agent (zinc
nitrate) into the micropores.
24 V.R. Batistela et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 513 (2017) 2027

Fig. 4. Micrographs of 10NaA catalyst at magnications of: (a) 1 micrometer and (b) 0.5 micrometers.

Fig. 5. TEM micrographs of the catalysts: (a) 10NaY and (b) 10USY.

Table 3 approaches pure oxide (Table 3), probably due to the highly recov-
Bandgap energy values of the catalysts, and the corresponding wavelengths in
ered surface of the zeolite.
nanometers (in brackets).
In the USY, the ZnO presence was not enough to modify signif-
NaA, eV (nm) NaY, eV (nm) USY, eV (nm) icantly the bandgap of the pure support (Table 3). Even the value
0%ZnO 2.97 (417.5) 4.69 (264.4) 3.75 (330.6) of pure ZnO is lesser than that of zeolite USY. In fact, all the cata-
5%ZnO 3.20 (387.5) 3.28 (378.0) 3.86 (321.2) lysts supported on USY exhibited very similar values. The absence
10%ZnO 3.16 (392.4) 3.23 (383.9) 3.80 (326.7) of bandgap changes by the presence of ZnO on USY probably came
ZnO = 3.20 eV (387.4). from the localization of the oxide inside the micropores rather than
on the external surface (Fig. 5).

3.5. Photoacoustic spectroscopy (PAS) 3.6. Zero point of charge (ZPC)

Fig. 6 shows the photoacoustic spectra of zeolitic catalysts that
allowed determining the bandgap of the photocatalyst.
It is clear that all pure zeolites have photoacoustic signal in the
ultraviolet region, while zeolite A also shows absorption in the visi-
ble region (Fig. 6). In the presence of ZnO, the photoacoustic spectra
show intensity increase and spectral displacement to the visible
region in comparison to pure zeolites. This occurs because the sup-
ported catalysts are hybrids of pure zeolites and ZnO. Thus, zeolites
surroundings undergo inuences in the oxide supported, which is
quite difcult to explain.
Table 3 shows the values of the bandgap. It can be seen that
pure zeolite NaA (2.97 eV) is the one that has the closest value to
ZnO bandgap (3.20 eV). Indeed, with ZnO, the 5NaA and 10NaA cata-
lysts present bandgap values close to the pure ZnO, which probably
results from the exposure of ZnO on the zeolite surface.
A different effect was found in zeolite NaY. Although the
bandgap value of the zeolite NaY is very high, in the presence of
impregnated ZnO the bandgap is considerably smaller. Its value
Knowledge of ZPC values allows evaluation of the average elec-
trostatic interactions among catalysts and chemicals in the medium
once ZPC refers to the pH in which a surface is electrically neu-
tral [78]. Even being electrically neutral, having pH = ZPC, a surface
can present acid and basic sites in equal number and behaves with
similar rates of adsorption for anionic and cationic species. When
pH < ZPC, the surface is electrically positive and tends to adsorb
negatively charged species, and vice versa. The experimentally
obtained ZPC values are shown in Table 4.
In the presence of ZnO, a signicant decrease in ZPC for NaA
system was observed, which suggests a synergic effect of ZnO in
the external area of the catalyst and zeolitic structure. In NaY and
USY catalysts, the ZPC values increased approaching the value of
pure ZnO (ZPC = 8.7), indicating that the ZnO acts as an integral
part of the structure of the catalysts, due to its incorporation into
the pores.
Additionally, the acidity of aluminosilicate minerals is closely
related to the proportion of Si and Al, constituents of its primary
 V.R. Batistela et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 513 (2017) 2027 25

1.2 structure. The Al and Si groups can receive or leave proton and,
ZnO depending on the pH of the medium, provide positive or negative
1.0 charge density on the surface [78]. As shown in Table 4, the ZPC
values of pure zeolites follow the same trend of the Si/Al ratio. By
presenting higher Si content, acid sites prevail in the zeolite USY
Photoacoustic signal

0.8 10NaA
and its surface requires a low pH value (less than 3) to have an
excess of positive charges. On the other hand, the zeolite NaA is the
5NaA most basic of all and it is presented with excess of negative charge
0.6
only at higher pH (pH > 9.4). However, the catalysts efciency is
not related only to the sites electric charge on surface, but also the
0.4
surface area and hydrophobic characteristics.
NaA
0.2
3.7. Comparison of the properties of the catalysts

0.0 The catalysts supported in NaA maintains several ZnO properties

200 300 400 500
at 5 and 10% of the oxide, and they can be used in heterogeneous
wavelength (nm) photocatalysis due to the lower amount of ZnO taking advantage
of the high crystallinity conferred by the zeolites that makes the
catalyst removal easier.
1.2
The catalysts supported on USY has higher bandgap values com-
pared to ZnO, which requires a powerful UV radiation source,
1.0 making the phototreatment difcult. However, once the supported
ZnO catalysts show low ZPC, and high specic surface area, they can be
0.8 interesting for the removal of positively charged pollutants.
Photoacoustic signal

The fact that the ZnO/NaY catalysts and pure ZnO have almost
equal ZPC indicates similar catalyst-substrate interaction. How-
0.6
ever, the supported ZnO on NaY exhibits higher specic area
reaching more than 20-fold of ZnO area. This increased area favors
0.4
10NaY
the adsorption and probably makes the attack of oxidative species
easier, thus enhancing the photocatalytic efciency.
5NaY
0.2
NaY 4. Conclusions
0.0
200 300 400 500 The impregnation of ZnO in zeolites can favor its applications
wavelength (nm) in heterogeneous photocatalysis. In this sense, it should avoid the
process trial and error as experimental design when one photocata-
1.2
lyst is investigated. The XRD, TEM, PAS and ZPC techniques allowed
determining some important characteristics that pointed out ZnO
supported in zeolites as possible efcient catalysts.
1.0 Analyses of atomic absorption revealed the difculties in the
ZnO
synthesis of catalysts with precise levels of ZnO. Oxide impregna-
Photoacoustic signal

0.8 tion occurred within the micropores, decreasing the specic area
compared to the pure zeolites. For the ZnO/NaA, as the micropore
volume is small, the full cavity saturation occurs and crystallization
0.6
10USY also occurred on the external surface of the catalyst. In general, all
of the proposed catalysts may be alternatives instead of pure ZnO in
0.4 photocatalysis. Of course, it depends on the type of pollutant to be
degraded, the electrostatic pollutant-catalyst interaction and the
0.2
experimental conditions.
USY
5USY
0.0
Acknowledgments
200 300 400 500
wavelength (nm) This work was sponsored by the Brazilian funding agencies
Unidade Gestora do Fundo Paran UGF (SETI/PR) and Conselho
Fig. 6. Photoacoustic spectra of the catalysts of ZnO supported on NaA, NaY and Nacional de Desenvolvimento Cientco e Tecnolgico (CNPq).
USY.

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