J Mater Sci (2013) 48:67786785

DOI 10.1007/s10853-013-7482-7

TiO2/clinoptilolite composites for photocatalytic degradation

of anionic and cationic contaminants
M. E. Trujillo D. Hirales M. E. Rincon
J. F. Hinojosa G. L. Leyva F. F. Castillon

Received: 30 March 2013 / Accepted: 27 May 2013 / Published online: 7 June 2013
 Springer Science+Business Media New York 2013

Abstract The present work aims to study the bulk and

surface properties of the TiO2/clinoptilolite composite on
the crystalline structure, superficial area, bandgap energy,
zeta potential, particle size distribution, and chemical
composition; in order to analyze the effect of the clinoptilolite proportion in the photocatalytic degradation of
pollutants. TiO2/clinoptilolite composites were prepared by
adding different mass proportions of clinoptilolite to a sol
gel bath containing TiCl4 as the titania precursor. Surface
charge studies explain the larger sensitivity to composite
ratio observed in the photocatalytic degradation of anionic
pollutants than in cationic dyes. An optimum TiO2/clinoptilolite ratio of 90/10 was found to be the most efficient
in terms of lower tendency to agglomeration, largest surface area, and increased crystallite size. Improvement in
composite surface area occurs only at low clinoptilolite
wt% and seems to be caused by lower agglomeration of
nanometric TiO2 and acid-induced porosity in the zeolite.

M. E. Trujillo (&)  D. Hirales  J. F. Hinojosa  G. L. Leyva

Department of Chemical Engineering and Metallurgy,
Universidad de Sonora, Blvd. Luis Encinas y Rosales, CP 83000,
Hermosillo, Sonora, Mexico
e-mail: mariat@iq.uson.mx
M. E. Rincon
Institute of Renewable Energies, UNAM, Apartado Postal 34,
62580 Temixco, MOR, Mexico
F. F. Castillon
Universidad Nacional Autonoma de Mexico, CNyN, km 107,
Carretera Tijuana-Ensenada Apdo Postal 14, CP 22800,
Ensenada, B.C., Mexico

123

Introduction
Heterogeneous photocatalysis is an advanced oxidation
process (AOP), which can be successfully used to oxidize
pollutants present in aqueous systems. It consists of the use
of a semiconductor material that absorbs light and generates e- and h? pairs. Migration of these carriers to the
semiconductor surface can degrade the pollutant directly or
produce powerful oxidants, such as the OH radicals. This
AOP has become a very attractive technology in the
removal of contaminants, because it is an environmentally
friendly process and has the possibility of using solar
energy as the energy source. Some aspects that have been
studied to improve the photocatalytic degradation performance are immobilization on large area supports to
increase photocatalyst dispersion, and metal doping to shift
the photoactivity to longer wavelengths [17]. Deposition
on solid supports like glass, silica, stainless steel, and
zeolites (clinoptilolite, chabazite, mordenite, etc.) is also
appealing because it facilitates the recovery and reutilization of the semiconductor nanoparticles. In particular,
clinoptilolite is a natural and abundant zeolite, with 50 %
porosity and great adsorption capability [8], and has been
used successfully as TiO2 support [915]. Moreover, TiO2/
clinoptilolite composites were used for the adsorption and
photocatalytic degradation of industrial basic dye (MV-2B)
in a chemical reactor coupled to a solar CPC concentrator
[15]; here the authors found that regardless of the superior
adsorption kinetics of 1/99 and 10/90 TiO2/clinoptilolite
composites, the composites with weight proportion of 99/1
and 90/10 provided better photocatalytic performance.
Other studies [10, 14] have found that for the degradation
of anionic acid dyes, the largest degradation per unit
weight of semiconductor material is observed in diluted
composites with 215 wt% of TiO2.

J Mater Sci (2013) 48:67786785

The present work aims to study the bulk and surface

properties of the composite materials in more detail, and to
determine the surface interaction between TiO2 and clinoptilolite, and the effect of the TiO2/clinoptilolite ratio on
the crystalline structure, superficial area, bandgap energy,
chemical composition, particle size distribution, and surface charge.

Materials and methods

Composite preparation
TiO2 was synthesized by the solgel technique at low
temperature (\10 C) by adding TiCl4 (Alfa Aesar 98 %)
drop by drop to 1 M HCl (Fermont) solution. Immediately
after TiCl4 addition the pH was adjusted to 3 with concentrated NH4OH (Fermont 29.1 %), keeping the solution
under strong stirring for 24 h to obtain a very stable milky
solution. Oxohydroxy titania precipitates (TiO(OH)nH2O)
were obtained by sol neutralization with concentrated
NH4OH (Fermont 29.1 %). The precipitates were washed
abundantly with distilled water and dehydrated at 100 C.
For composites, a similar procedure was followed except
that a proper amount of clinoptilolite was dispersed in the
acid solution before TiCl4 addition, to obtain different
weight ratios of catalysts/adsorbent (TiO2/clinoptilolite):
1/99, 10/90, 50/50, 90/10, and 99/1. Finally, all the catalysts (with and without clinoptilolite) were heated at
400 C for 1 h.
Characterization techniques
The crystalline structure of the samples was obtained by
X-ray diffraction (XRD) using a Gerflex D/max-B (Rigaku)
instrument, with a Cu radiation source (Cu Ka) and a
graphite monochromator; the diffraction patterns were taken
over the 2h range of 560. The microstructural and morphological characterization were obtained using scanning
electron microscopy (SEM) with X-ray microanalysis
(JEOL JSM5300), and transmission electron microscopy
(TEM) (Jeol-200CX TEM) with an acceleration voltage of
200 kV. Particle size distribution measurements were
acquired from a Coulter LS 100Q (Beckman) system with a
sensitivity of 400 nm948 lm. Surface analyses were
obtained from nitrogen adsorption isotherms carried out in a
Micromeritics Gemini 2360 system, where the samples were
degassed at 200 C for 6 h. The chemical composition and
type of bonding of the composite constituents were elucidated from FT-IR spectroscopy (Perkin Elmer 1600),
whereas for band-gap determination an UVVis spectrophotometer (Varian Cary 300) equipped with an integration
sphere was used in the diffuse reflectance mode; the scanning

6779

velocity of the spectrophotometer was 100 nm min-1 in the

200800 nm range. Finally, the surface charge of the materials and its zeta potential were measured with a Zeta Meter
System 3.0 over the pH range from 4 to 10 at 25 3 C
using 0.01 M NaNO3 as the ionic salt.
Photocatalytic process
The photocatalytic degradation of MV-2B dye and cyanide
was conducted in Vycor lidded crucibles of 50 ml, maintaining the solutions at constant agitation. The light source
was a monochromatic UV lamp (365 nm) with a power of
18 W. The dye was in a 40 ml neutral solution to avoid
structural modifications with pH changes (typical of triphenylmethanes). The initial concentration of MV-2B was
3 9 10-5 M with 0.04 mg of photocatalyzer. For the photocatalytic degradation of cyanide, the samples were synthetic solutions of NaCN (100 mg L-1) corresponding to
53 mg L-1 of CN- at pH 11. All the solutions of CN- were
valued by titration with AgNO3, which is utilized to determine free cyanide in concentrations up to 1 mg L-1 [16].

Results and discussion

Materials characterization
Figure 1 shows the XRD patterns of pure clinoptilolite
and the composites TiO2/clinoptilolite with the following
mass proportions: 99/1, 90/10, 50/50, 10/90. For composites with TiO2 content larger than 10 wt%, the presence of
anatase is evident (Fig. 1ac), whereas, for clinoptilolite
peaks to be noticeable the wt% must be around 50 or higher
(Fig. 1cd), confirming the growth of titania on the clinoptilolite surface. Table 1 shows the average crystallite
size of TiO2, which is estimated from the full-width at halfmaximum (FWHM) of the diffraction peak at 2h = 48
using the DebyeScherrer formula (this peak was selected
because it doesnt overlap with clinoptilolite). The results
suggest that the presence of clinoptilolite promotes the
nucleation and growth of the semiconductor crystallites.
SEM micrographs of these samples are shown in Fig. 2,
where the presence of large agglomerates (around 300 nm
in diameter) is evident in samples with low content of
clinoptilolite. Apparently, clinoptilolite acts as a dispersant
to avoid the typical tendency of nanometric TiO2 to form
agglomerates [17, 18]. These agglomerations are more
visible in the TEM images presented in Fig. 3, where TiO2
particles of 68 nm (dotted circles) and clusters of
approximately 300 nm can be found in the composites. The
particle size distribution analysis confirms that 90 % of the
agglomerates in all composites have sizes between 375 and
420 nm. The analysis was made with the material in

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J Mater Sci (2013) 48:67786785

Fig. 1 XRD patterns for composites TiO2/clinoptilolite: a 99/1, b 90/

10, c 50/50, d 10/90 prepared by the solgel method after thermal
treatment in air at 400 C and e clinoptilolite

Table 1 Average diameter sizes of TiO2 (nm)

Sample

Diameter particle (nm)

48

TiO2

6.3

Composite 99/1

7.4

Composite 90/10

7.6

Composite 50/50

8.5

22.5

Composite 10/90

16.1

Clinoptilolite

16.2

suspension and may indicate the real active area during the
photocatalytic degradation carried out with the semiconductor in suspension. Therefore, the 90/10 ratio could give
a composite with a superior surface area because of the
lower amount and size of its agglomerates.
The results of the BET superficial area analysis shown in
Table 2, confirm the above conclusion. At low concentration of clinoptilolite, there is an increase in surface area
that reverts at clinoptilolite content larger than 10 wt%.
Interestingly, the surface area does not follow a linear
relationship between the ratios of the two components, but
at least qualitatively it seems a strong function of crystallite
size and tendency to agglomerate. The composite with the
proportion 90/10 has again proven to be the proper relationship with the largest surface area, and some of this area

123

undoubtedly comes from its lowest tendency to agglomerate; this composite ratio has also been reported as the
optimum one with other support materials [1922].
Table 3 presents the quantitative analysis of the atomic
composition obtained with EDS. Literature reports suggest
that acid treatments cause the removal of aluminum from
zeolites, which could lead to an increase in clinoptilolite
surface area. Indeed, at large TiO2 content EDS results show
a Si/Al ratio very different than the one observed in natural
clinoptilolite. Composites with low TiO2 concentration keep
a Si/Al ratio close to natural clinoptilolite despite the low pH
of the TiO2 synthesis. Therefore, the acid induced porosity of
clinoptilolite is another factor to be considered in the
increased surface area of the 90/10 composite.
FTIR studies also confirm the EDS results. Figure 4
shows the infrared spectrum of TiO2 and clinoptilolite, and
Fig. 5 corresponds to TiO2/clinoptilolite composites. In the
spectrum of clinoptilolite, the most intense bands appear at
10401100 cm-1 and correspond to OSi(Al)O bond
vibrations; the band around 1053 cm-1 is due to the external
tetrahedra linkage asymmetric stretching and is very sensitive to the dealumination degree [23]. The deformation
stretches, symmetric tetrahedral stretching, and double ring
vibrations of bonds AlOAl and SiOSi are observed in
the bands 460, 676, and 608 cm-1, respectively. The isolated
band peaked at 1640 cm-1 is due to bending vibrations of
sorbed water. In addition, the band between 3680 and
3450 cm-1 are attributed to the bridging OH groups in Si
OHAl, and results from the location of hydrogen atoms on
different oxygen atoms of the framework. Figure 4 also
shows the TiO2 spectrum with the characteristic double peak
at the region of 500700 cm-1, which can be associated to
the stretching vibration of TiO and TiOTi bonds. The
signal of terminal titanol groups (TiOH moieties), commonly referred to as dissociatively adsorbed H2O, is centered at 3400 cm-1 and the signal of hydroxyl groups of
physisorbed H2O, located at 3200 and 1640 cm-1, appear
more intense than the one observed in clinoptilolite.
Figure 5 shows the infrared spectra of TiO2/clinoptilolite composites. The bands at 1053, 460, and 608 cm-1 are
related with AlOAl and AlOH bonds, and the intensity
differences corroborate that aluminum leaching is not
evident in composites with low TiO2 content, but could be
an issue in those with larger TiO2/clinoptilolite ratio. In the
90/10 and 99/1 composites there is a new band at
1160 cm-1 related to NH bonds, which indicates that
some amount of NH4? incorporates during the synthesis by
ion exchange, perhaps due to the high permanent negative
charge density of zeolites and the presence of inner
channels for ion diffusion [24, 25].
To determine the effect that the chemical and structural
differences have on the optical properties of the composites,
the onset of absorption (directly correlated to the energy

J Mater Sci (2013) 48:67786785

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Fig. 2 Images of SEM (92000)

(a) TiO 2

(b) 99/1

(c) 90/10

(d) 50/50

(e) 10/90

(f) 1/99

(g) clinoptilolite

band gap) was obtained by in situ UVVis diffuse reflectance spectroscopy (UVVis-DRS), using the first derivative
of the equation for optical transitions [26]:
dlnahm = dhm m=hm  Eg

where a is the absorption coefficient, Eg is the band gap of

the semiconductor, and m represent the nature of optical

transition (m 0:5 for direct transition). Table 4 summarizes the energy band gap of the considered materials; it
can be observed that small quantities of clinoptilolite cause
a shift in the energy band gap of TiO2 in agreement with
the increase in crystallite size observed by XRD. For proportions of clinoptilolite over 50 %, the onset of absorption
is not only correlated to the energy band gap of TiO2, but

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50 nm

J Mater Sci (2013) 48:67786785

(a)

200 nm

(b)

Table 3 Quantitative analysis with EDS

Sample

Ti

TiO2

33.33

66.67

Composite 99/1

32.51

66.79

0.21

0.34

1.62

Composite 90/10

29.51

67.67

0.6

1.87

3.12

Composite 50/50

12.61

73.71

11.27

5.64

Composite 10/90

2.4

77.23

2.67

16.94

6.34

Composite 1/99

0.22

77.86

2.7

18.09

6.70

77.32

2.87

17.77

6.19

Clinoptilolite

(c)

(d)

20 nm

20 nm

(e)

(f)

Fig. 3 Images of TEM for a pure TiO2, b clinoptilolite, composites

TiO2/clinoptilolite: c 99/1, d 90/10, e 10/90, and f 1/99
Table 2 BET superficial area
Sample

Superficial area (m2 g-1)

TiO2

124

Composite 99/1

144

Composite 90/10

189

Composite 50/50

128

Composite 10/90

76

Composite 1/99

27

Clinoptilolite

16

also to screening effects caused by the zeolite. Nevertheless, the tendency toward larger values of Eg suggest the
growth of highly dispersed TiO2 nanoparticles inside

123

Al

Si

Si/Al

confined environments (i.e., zeolite pores), which are not

evident from XRD, SEM, or TEM data. No doping effects
leading to optical sensitization were evident due to aluminum or ammonia incorporation, as was the case in TiO2
composites based on carbon black [22].
The zeta potential provides a quantitative measure of the
charge of colloidal particles in liquid suspension. The zeta
potential values reported for clinoptilolite surfaces indicate
negative surface charges increasing linearly in the pH
range of 212; while, the TiO2 in water is reported
amphoteric and could be positively charged or negatively
charged depending on the pH of the solution [27, 28].
However, the measurements that were carried out for TiO2
alone differ from those reported, as can be observed in
Fig. 6. The surface charge of TiO2 is similar to clinoptilolite, because it retains negative charge in a broad range of
pH. The above behavior can be explained by the synthesis
method of TiO2, which permits the presence of OH- ions
on the material surface, as was reported in a previous study
[22], besides OH- ions increase with pH and they can
adhere to the material surface increasing its negative
charge.
On the other hand, the analysis of TiO2/clinoptilolite
composites indicates that they (except the one with 1/99
composition) seem to have two directions of charge
migration. However, clinoptilolite and TiO2 present two
different migration velocities due to differences in charge,
size, and shape. The migration of the particle to the bulk of
the electric field is faster with a larger charge/size ratio.
Furthermore, no bonds formed between clinoptilolite and
the semiconductor, presenting an individual behavior in the
suspension. The highly diluted 1/99 composites, maintains
a more negative charge than clinoptilolite with inverse
tendency (the negative charge diminishes with pH), this
may be explained by considering that the increase of pH
promotes the lixiviation of the TiO2 trapped in the clinoptilolite structure, leaving the clioptilolite surface with
less negative charge.
From the results, it is clear that clinoptilolite proportion
in the composite materials leads to a different surface
potential. It is relevant to notice that surface charge
can influence the photocatalytic degradation of ionic

J Mater Sci (2013) 48:67786785

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Fig. 4 Infrared spectrum of

TiO2 and clinoptilolite

Fig. 5 Infrared spectrum of

TiO2/clinoptilolite composites:
a 99/1, b 90/10, c 50/50, d 10/
90, e 1/99

Table 4 Energy band gap (Eg) of TiO2 in composite materials

Sample

Absorption threshold (eV)

TiO2
Composite 99/1

3.40
3.35

Composite 90/10

3.33

Composite 50/50

3.40

Composite 10/90

3.70

Composite 1/99

3.90

contaminants. This was verified by the photocatalytic

degradation of cyanide, an anionic contaminant, which is
presented in Fig. 7, and the degradation of the cationic dye
MV-2B, presented in Fig. 8.
Figure 7 shows the degradation data normalized by the
total weight of the composite, with TiO2 removing 92 % of

Fig. 6 Potential Zeta analysis for Clinoptilolite, 1/99 composite, and

pure TiO2

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J Mater Sci (2013) 48:67786785

larger sensitivity to composite ratio with anionic pollutants

than with cationic dyes.
Research Highlights

Fig. 7 Effect of TiO2/clinoptilolite ratio on photocatalytic degradation of cyanide. pH 11, irradiation time = 20 h

We studied TiO2/clinoptilolite system used for

photocatalysis.
The proportion of composite was varied modifying
physical and optical properties.
The clinoptilolite proportion in the composite materials
leads to a different surface potential.
The surface charge can influence the photocatalytic
degradation of ionic contaminants.
The 90/10 proportion presents the best conditions for the
photocatalytic degradation of cationic contaminants.

Acknowledgements The authors acknowledge the technical assistance of Israel Gradilla M. and Eric Flores A. from CNyN-UNAM, as
well as financial support from CONACYT-Mexico through fellowships for Dzoara Hirales Salazar and Lizeth G. Soriano Leyva and
projects CB-2007-01-79743 and DGAPA-PAPIIT IN207511.

References

Fig. 8 Effect of TiO2/clinoptilolite ratio on photocatalytic degradation of MV-2B. pH 7, irradiation time = 80 s

cyanide, while the composites 90/10 and 99/1 eliminated

68 and 64 %, respectively (i.e., more than 10 or 1 %
reduction). In contrast to the photocatalytic degradation of
anionic pollutants, the degradation performance of MV-2B
dye at neutral pH appears similar for all composites except
for the 1/99 ratio. Figure 8 shows the elimination of MV2B dye, although the 99/1 composite has the best performance, the difference among the composites is \30 %.

Conclusions
The preparation and detailed characterization of TiO2/clinoptilolite composites are reported. An optimum TiO2/clinoptilolite ratio of around 90/10 was found to be the most
efficient in terms of lower tendency to agglomeration, largest
surface area, and increased crystallite size. Improvement in
surface area occurs only at low clinoptilolite wt%, and seems
to be the result of lower agglomeration of nanometric TiO2
and acid-induced porosity in the zeolite. Surface charge
influences the performance of the composites, which show a

123

1. Wu HC, Lin YS, Lin SW (2013) Int J Photoenergy

2. Fatimah I (2013) Disinfect Bull Chem React Eng Catal 7(3):191.
doi:10.9767/bcrec.7.3.4047.191-197
3. Carvalho GC, Foletto EL, Jahn SL, Villetti MA (2012) J Environ
Manage 98:107
4. Fu Y, Sun D, Chen Y, Huang R, Ding Z, Fu X, Li Z (2012)
Angew Chem 124:3420
5. Krejckova S, Matejova L, Koc K, Obalova L, Matej Z, Capek L,
Solcova O (2012) Appl Catal B 111112:119. doi:10.1016/j.apcatb.
2011.09.024
6. Khakpash N, Simchi A, Jafari T (2012) J Mater Sci 23:659. doi:
10.1007/s10854-011-0466-y
7. Khezrianjoo S, Doddarevanna Revanasiddappa H (2013) J Catal
8. Kowalczyk P, Sprynskyy M, Terzyk AP, Lebedynets M, Namiesnik
J, Buszewski B (2006) J Colloid Interface Sci 297:77
9. Khodadoust S, Sheini A, Armand N (2012) Spectrochim Acta,
Part A 92:91
10. Ilinoiu EC, Pode R, Manea F, Colar LA, Jakab A, Orha C, Ratiu
C, Lazau C, Sfarloaga P (2013) J Taiwan Inst Chem Eng 44:270
11. Ochieng A, Pambi RLL, Netshitangani P, Akach J, Onyango MS
(2012) J Sustain Dev Environ Prot 2:36
12. Li F, Jiang Y, Yu L, Yang Z, Hou T, Sun S (2005) Appl Surf Sci
252:1410
13. Nikazar M, Gholivand K, Mahanpoor K (2007) Kinet Catal
48:214
14. Nikazar M, Gholivand K, Mahanpoor K (2008) Desalination
219:293
15. Trujillo Camacho ME, Garca C, Hinojosa JF, Castillon FF
(2010) Revista Mexicana de Ingeniera Qumica 9:139 (ISSN
1665-2738)
16. Eaton AD, Clesceri LS, Greenberg AE, Franson MAH (1998)
Standard methods for the examination of water and wastewater.
American Public Health Association, Washington, DC
17. Yang-hsin S, Cheng-han L (2012) Environ Sci Pollut Res
19:1652

J Mater Sci (2013) 48:67786785

18.
19.
20.
21.

Yu J, Zhao X, Zhao Q (2000) Thin Solid Films 379:7

Ming C, Wu P (2005) Chin J Geochem 24:370
Paul B, Martens WN, Frost RL (2012) Appl Clay Sci 57:49
Arana J, Dona-Rodrguez JM, Tello Rendona E, Garriga i Caboa
C, Gonzalez-Daz O, Herrera-Melian JA, Perez-Pena J, Colon G,
Navo JA (2003) Appl Catal B 44:161
22. Rincon ME, Trujillo-Camacho ME, Cuentas-Gallegos AK (2005)
Catal Today 107108:606
23. Holmberg BA, Wang H, Yan Y (2004) Microporous Mesoporous
Mater 74:189

6785
24. Mingyu L, Xiaoqiang Z, Fenghua Z, Gang R, Gang C, Lin S
(2011) Desalination 271:295
25. Rozic M, Cerjan-Stefanovic S, Kurajica S, Vancina V, Hodzic E
(2000) Water Res 34:3675
26. Caruta BM (2006) Focus on nanomaterials. Research Nova Science Publishers Inc., New York, p 64
27. Kurama H, Karaguzel C, Mergan T, C
elik MS (2010) Desalination 253:147
28. Wanga X, Ozdemir O, Hampton MA, Nguyen AV, Do DD (2012)
Water Res 46:5247

123

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