ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2015, Vol. 89, No. 13, pp. 2432–2437.

© Pleiades Publishing, Ltd., 2015.

PHYSICAL CHEMISTRY OF NANOCLUSTERS

AND NANOMATERIALS

Synthesis and Characterization of ZnO–TiO2 Nanopowders Doped

with Fe via Sol–Gel Method and Their Application in Photocatalytic
Degradation of Anionic Surfactant1
M. Giahia,*, S. Saadat Niavolb, H. Taghavia, and M. Meskinfama
aDepartment of Chemistry, Lahijan Branch, Islamic Azad University, Lahijan, Iran
b
Department of Physics, Lahijan Branch, Islamic Azad University, Lahijan, Iran
*e-mail: giahi_m@yahoo.com
Received December 1, 2014

Abstract—ZnO and 0, 5, and 10 mol % Fe-doped ZnO–TiO2 nanopowders were synthesized by the sol–gel
Pechini method. The successful synthesis of coupled ZnO–TiO2 nanopowders was evident by XRD. Scan-
ning electron microscopy (SEM) revealed that the Fe ions were well incorporated into the ZnO–TiO2 crystal
lattice. The photocatalytic degradation of anionic surfactant (linear alkylbenzene sulfonate (LABS), was
investigated in aqueous solution using ZnO and Fe-doped ZnO–TiO2 nanoparticles. The degradation was
studied under different conditions such as the Fe3+ concentration, amount of photocatalyst, irradiation time,
pH, initial concentration and presence of electron acceptor. The results showed that photocatalytic degrada-
tion of LABS was strongly influenced by these parameters. The best conditions for the photocatalytic degra-
dation of LABS were obtained. It is found that under UV light irradiation, Fe-doping of ZnO–TiO2 increases
the efficiency of its photocatalytic activity in degradation of LABS than pure ZnO and ZnO–TiO2.

Keywords: Fe-doped ZnO–TiO2, photocatalytic degradation, sol–gel method, surfactant, Pechini method.
DOI: 10.1134/S0036024415130154

INTRODUCTION decompose a large number of organic and inorganic

Recently, semiconductor nanocrystals have been
extensively studied due to their size tunable physical
and chemical properties. ZnO is II–VI compound
semiconductor, has a wide band gap of 3.37 eV and a
large exciton binding energy of 60 mV at room tem-
perature [1]. Zinc oxide continues to attract attention
for its unique properties and various applications such
as transparent conducting oxides, ultra-violet lasers,
light modulators, anti reflective coatings, mechanical
actuators, sensors and solar panel displays [2, 3]. In
particular, ZnO has attracted much attention with
respect to the degradation of various pollutants due to
its being relatively cheap, stability and high photoca-
talysis [4–6]. One of the main problems associated
with the feasibility and viability of ZnO semiconduc-
tor photocatalytic oxidation is represented by a high
tendency of photoinduced hole-electron pairs to
recombine, which implicates deactivation of the pho-
tocatalyst [7]. Furthermore, among the semiconduc-
tors being studied, TiO2 is one of the most efficient
photocatalysts as it is a stable and an inexpensive pho-
tosensitive material. One of the most intriguing appli-
cation areas of titanium dioxide is photocatalytic
activity for environmental protection, since it can
1 The article is published in the original.
pollutants. Recently, much interest has been devoted
to the use of TiO2-based photocatalysts for the degra-
dation of dyes in aqueous solutions [8]. However, pure
TiO2 exhibits low photocatalytic property due to rapid
charge carrier recombination. Various strategies have
been adopted for improving the photo-excited charge
separation and to enhance the photocatalytic activity
by modifying the surface or bulk properties of a photo-
catalyst, such as deposition of metals, doping, surface
chelation, and coupling of two semiconductors [9].
Among the coupled semiconductors, many efforts
have been devoted to combine TiO2 with other metal
oxides such as ZnO, SnO2, Fe2O3, ZrO2, Cu2O, etc. In
addition to these, the most promising method to
increase the photocatalytic efficiency is the surface
modification of coupled semiconductor. The surface
modification of coupled semiconductor can be
achieved by metal doping into them. Recently TM
(transition metal)-doped II–VI and III–V compound
semiconductors have been extensively studied (such as
Fe, Co, Ni, Mn, etc.) [10]. Various methods are avail-
able for the preparation of photocatalysts, such as
electrochemical [11], wet chemical [12], precipitation
[13], and sol–gel [14]. Sol–gel is one of the most
exploited methods; it is used mainly to produce thin
film and powder catalysts. In comparison with other

2432
 SYNTHESIS AND CHARACTERIZATION of ZnO–TiO2 NANOPOWDERS
oxide preparation methods, the polymerized complex
or modified sol–gel method designed by Pechini [15]
is a low temperature synthesis route which can pro-
duce a more uniform particle distribution. The poly-
meric precursors were prepared using zinc acetate and
a mixed solution of citric acid and ethylene glycol as a
chelating agent and reaction medium, respectively.
However, there were few studies on the synthesis of
photocatalytic properties of Fe-doped ZnO–TiO2
nanoparticles prepared by the sol–gel process. In this
study, the nano-scale Fe-doped ZnO–TiO2 coupled
oxide photocatalyst has been synthesized by the sol–
gel Pechini method. The synthesized powders were
characterized by XRD and SEM. Photocatalytic activ-
ity was determined by means of degradation of anionic
surfactant (sodium alkylbenzene sulfonate) under UV
light irradiation.
EXPERIMENTAL
Chemicals
Zinc nitrate hexahydrate (Zn(NO3)2 · 6H2O), tita-
nium (IV) isopropoxide (TTIP), iron sulfate (FeSO4),
ethylene glycol(C2H6O2), citric acid, K2S2O8, are cho-
sen as starting materials. Linear alkylbenzene sulfon-
ate (LABS) was obtained from Merck. The surfactant
shows an adsorption maximum of 223 nm. All reagents
were used as supplied by the manufacturers without
further treatment.
Preparation of ZnO
Two solutions were prepared by dissolving separately
measured amount of zinc nitrate and citric acid into
25 mL of ethylene glycol and deionized water. The con-
centration of prepared solutions was set at 0.4 M. After
complete dissolution of the precursors, citric acid solu-
tion was added to zinc nitrate solution. The obtained
mixture was stirred at 80°C for 4 h to yield a clear and
homogeneous solution. Afterwards sol was slowly cooled
in air down to room temperature and then aged for 24 h.
Following this, the sample was placed into a tube furnace
and annealed in air at 700°C for 2 h.
Preparation of Fe-doped ZnO–TiO2 Nanopowders
ZnO–TiO2 nanopowders with different concentra-
tions of Fe doping (0, 5, and 10 mol %) were synthe-
sized via sol–gel technique. Two solutions were pre-
pared by dissolving separately measured amount of
zinc nitrate and citric acid into 25 mL ethylene glycol
and deionized water. After 10 min TTIP was dissolved
in zinc nitrate solution. Subsequently, an aqueous
solution of citric acid was added in turn into the above
solution under vigorous stirring at 80°C, after 30 min
iron sulfate was added in to solution as dopant mate-
rial. The dopant stoichiometry was controlled by dis-
solving proper amount of iron sulfate. The Fe : Zn or
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 89
2433
Fe : Ti ratio in solution was changed from 0 to
10 mol %. The concentration of the as prepared solu-
tions was set at 0.4 M. The obtained mixture was
stirred at 80°C for 4 h to yield a clear and homoge-
neous solution. Then sols were slowly cooled in air
down to room temperature and then aged for 24 h. The
obtained samples were placed into a tube furnace and
annealed in air at 700°C for 2 h. The powders X-ray
diffraction (XRD) patterns of the samples were
recorded on a BRUKER D8 ADVANCE X-ray dif-
fractometer using CuKα radiation. Microstructures,
morphologies and element content were studied using
JSM-6700F scanning electron microscope (SEM).
Photodegradation experiments were performed with a
photocatalytic reactor system under the irradiation of
a UV lamp.
Photocatalytic Activity Measurements
Photocatalytic testing was conducted in a thermo-
static cylindrical Pyrex reactor with a 50 mL capacity.
A 400-W mercury lamp, with a major emission at
223 nm, was used as the UV light source. In a 50 mL
flask, 25 mL of LABS solution with an initial concen-
tration range of 20 mg/L was placed. A known amount
of Fe-doped ZnO–TiO2 nanopowder was added to the
surfactant and oxidant. The pH of solution was
adjusted by diluted HCl and NaOH solutions. The
mixture was irradiated with the UV lamp for 4 h. The
aqueous suspension was magnetically stirred (speed of
80 rpm) throughout the experiment. 5 mL samples
were withdrawn on regular intervals of time and cen-
trifuged. Absorbance of the supernatant solution was
measured and returned to the reactor. The quantitative
estimation of the surfactant was carried out using a
UV–Vis spectrophotometer (Jenway 6405) at λmax =
223 nm. The degree of photodegradation (X) as a
function of time is given by the following relationship
X = (C0 – C)/C0,
where C0 is the initial concentration of surfactant, and
C the concentration of surfactant at time t.
RESULTS AND DISCUSSION
Characterization of Fe-Doped ZnO–TiO2 Nanopowders
The crystal structures of ZnO and Fe-doped ZnO
were characterized using XRD. Figure 1 shows the
XRD pattern of pure ZnO and 0, 5, and 10 mol % Fe-
doped ZnO–TiO2 nanopowders. For pure ZnO the
diffraction peaks are quite matching with the hexago-
nal wurtzite ZnO data. In ZnO–TiO2 sample however,
the intensities of ZnO diffraction peaks decrease and
one extra diffraction peak (2θ = 27.39°) from
Ti-related second phase was observed. The successful
doping of the Fe element into the ZnO–TiO2 host was
evident by XRD lines. But the wurtzite structure is
modified by the addition of Fe into ZnO–TiO2 host
No. 13 2015
2434 GIAHI et al.

(311)
10 mol % Fe-doped ZnO−TiO2
(220) (511) (440)
(110)
(400) (422) (533)

(311)

Intensity, arb. units

5 mol % Fe-doped ZnO−TiO2
(440)
(220) (511)
(110) (400) (422) (533)

(002)
ZnO−TiO2
(100) (110)
(002) (103) (112)
(110) (102)
(201)
(200) (004) (202)

(002)

(100) (110)
(002) (103) (112) ZnO
(102) (201)
(200) (202)
(004)

20 25 30 35 40 45 50 55 60 65 70 75 80
2θ, deg
Fig. 1. XRD patterns of prepared nanopowders: undoped ZnO, 0.0, 5.0, and 10% Fe-doped ZnO–TiO2.

material. It can be seen that the Fe-doped ZnO–TiO2 exhibited a porous microstructure and spherical crys-
sample exhibit two phases with TiO2 and ZnFe2O4 talline surface particles. However, at 10% Fe-doped
structure. From Fig. 1, it also can be seen that the sample uneven surface and dense microstructure can
XRD peaks of Fe-doped ZnO–TiO2 were broadened be distinguished.
comparing with the pure ZnO. Two factors contribute
to this phenomenon. On one them, it can be attributed Degradation of Surfactant in the Presence of a Series
to the smaller crystal size of Fe-doped ZnO–TiO2. of Fe-Doped ZnO–TiO2, ZnO–TiO2, and Pure ZnO
And other, doping Fe into the ZnO–TiO2 crystal lat-
tice can inhibit crystallization of the sample [16]. The curves of LABS degradation using ZnO,
ZnO–TiO2, and Fe-doped ZnO–TiO2 nanopowders
The crystallite size of the samples was estimated prepared with different Fe2+ contents as photocatalysts
from the Scherrer’s equation [17]: are shown in Fig. 3. It is found that under UV light
D= kλ , irradiation, all the Fe-doped ZnO–TiO2 nanopowders
β cos θ exhibit higher photocatalytic activity in degradation of
LABS than ZnO–TiO2. It indicated that the addition
where D is crystallite size, λ is the wavelength of CuKα of Fe2+ had improved the absorption capability of
radiation (λ = 0.154056 nm), β is the full-width at half ZnO–TiO2 toward UV light, possibly because increas-
maximum intensity, θ is Bragg’s diffraction angle, and ing of the particle diameter, the chance of recombina-
k is a constant. The average crystallite size was found tion for photoinduced electron-hole pairs increased
to decrease from 20.39 nm (pure ZnO) to 15.82 nm for because of their slow arrival to reaction sites at the sur-
10 mol % Fe-doped ZnO–TiO2 nanopowder. face [18]. The best photocatalyst in degrading of LABS
Scanning electron microscopy (SEM) is a conve- solution is 10 mol % Fe-doped ZnO–TiO2. The opti-
nient technique to study the surface morphology of mum degradation of LABS is 94% after 4 h reaction.
nanostructures. Figure 2 shows the SEM images of the
pure ZnO and 0, 5, and 10 mol % Fe-doped ZnO–
TiO2 nanopowders prepared by sol–gel Pechini Effect of UV, 10 mol % Fe-Doped ZnO–TiO2, and S 2O82 −
method. Undoped ZnO nanopowders exhibit spheri-
cal shape and some agglomerations are seen in the The effect of sulfate radical (SO •−
4 ) as an oxidant on
background. These images show that the aggregates the degradation of LABS was investigated and com-
contain both very small and large particles. Mean- pared with UV-irradiation only, UV/S 2O 82 − ,
while, the cluster size is strongly dependent on Iron UV/10 mol % Fe-doped ZnO–TiO2, and
concentration. As Fe content rises from 0 to 10 mol %,
the cluster size decreases slowly that confirms the UV/10 mol % Fe-doped ZnO–TiO2/S 2O 82 − systems.
XRD results. Generally, the low doping samples As it can be seen from Fig. 4, 10 mol % Fe-doped

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 89 No. 13 2015

 SYNTHESIS AND CHARACTERIZATION of ZnO–TiO2 NANOPOWDERS 2435

(а) 1 μm (a) 300 nm

(b) 1 μm (b) 300 nm

(c) 1 μm (c) 300 nm

(d) 1 μm (d) 300 nm

Fig. 2. SEM images of nanocrystalline powders at different magnifications: (a) pure ZnO powders and Fe-doped ZnO–TiO2,
(b) 0% Fe, (c) 5% Fe, and (d) 10% Fe.

ZnO–TiO2 alone in the absence of sulfate radical and diation time. A similar behavior was also observed in
UV irradiation was found to have no measurable effect the UV system alone. In the case of sulfate radical
on the degradation of the surfactant during of 4 h irra- alone, the degradation yield was determined as
approximately 11% after 4 h for 20 mg/L. The degra-
dation yield of surfactant in UV/S 2O 82 − system without
Degradation, %
100 Fe-doped ZnO–TiO2 was obtained approximately
95 24% after 4 h treatment which is probably due to the
90 production of radical species. The photocatalytic
85 decomposition of peroxydisulfate potassium under
80 UV radiation involves the formation of a number
75
70 highly reactive radical (OH•, SO 4− ) and the non-radi-
65 cal species (O3, SO 24 − ) [19, 20] as shown in Fig. 4.
60 UV/Fe-doped ZnO–TiO2 system had more signifi-
55
50
cant effect on the degradation of surfactant than the
ZnO−TiO2/ ZnO−TiO2/ ZnO−TiO2
10% Fe 5% Fe
ZnO UV/S 2O 82 − system. This result is explained by the fact
Type of photocatalyst that Fe-doped ZnO–TiO2 is exposed to UV radiation,
Fig. 3. Photocatalyzed degradation of LABS in the presence an electron is promoted from the valence band to the
of a ZnO, ZnO–TiO2, and Fe-doped ZnO–TiO2 com- + −
pounds; 20 mg/L LABS, concentration of photocatalyst: conduction band. Thus hνB /e CB pairs is produced
0.2 g/L, 1 mM K2S2O8, irradiation time, 4 h, Vt = 25 mL. (Eq. (1)). The photocatalyst, Fe-doped ZnO–TiO2, is

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 89 No. 13 2015

2436 GIAHI et al.

UV only 100
UV/ZnO−TiO2−Fe 10% (5 mg) 90 0.12 g/L
UV/K2S2O8 (1 mM) 80 0.20 g/L
UV/ZnO−TiO2−Fe 10% (5 mg)/K2S2O8(1 mM)

Degradation, %
100 70 0.28 g/L
90 0.36 g/L
80 60
Degradation, %

70 50 0.44 g/L
60 0.52 g/L
50 40
40 30
30
20 20
10 10
0
0 60 120 180 240 0
Irradiation time, min 0 60 120 180 240
Irradiation time, min
Fig. 4. Degradation of LABS, initial concentration Fig. 5. Effect of catalyst concentration; 20 mg/L LABS,
20 mg/L. 1 mM K2S2O8, pH 6, irradiation time, 4h; Vt = 25 mL.

a wide band gap semiconductor, corresponding to cle in the solution. Hence, the rate of photodegrada-
radiation in the near-UV range tion decreases at the higher catalyst loading [23].
− +
Fe-doped ZnO–TiO2 + hν → e CB + hνB . (1)
+ Effect of Concentration of Surfactant
The highly oxidative hνB can react easily with surface
bound H2O to produce hydroxyl radicals or can The influence of initial surfactant concentration on
directly react with the surface adsorbed organic mole- degradation was examined in the range 10–50 mg/L at
cules (R) to form R+ [21, 22]. 0.2 mg/L catalyst loading and K2S2O8 (1 mM) under
+ UV irradiation. A representative concentration–time
hνB + H2O(ads) → OH• + H+, (2) profile is shown in Fig. 6. The rate of photodegrada-
Surfactant + OH → degradation products,
•
(3) tion of the surfactant decreased at higher concentra-
tions. With increasing the amounts of surfactant, more
+
Surfactant + Fe-doped ZnO–TiO 2 ( hν B ) surfactant molecules were adsorbed on the surface of
(4) the photocatalyst and the active sites of the catalysts
→ oxidation products,
were also reduced. Therefore, with increasing occu-
−
Surfactant + Fe-doped ZnO–TiO 2 (e CB ) pied sites of catalyst surface, the generation of hydroxyl
(5) radicals will be decreased. On the other hand, increas-
→ reduction produ cts, ing concentration of surfactant can lead to decreasing
when potassium peroxydisulfate was added to UV/Fe- the number of photons arrived to the surface of cata-
doped ZnO–TiO2 system. Surfactant degradation
increased from 44 to 94% after 4 h.
Degradation, %
100 10 ppm
Effect of Catalyst Concentration
90
In order to determine the effect of catalyst loading, 20 ppm
80
the experiments were performed by varying catalyst 70 30 ppm
concentrations from 0.12 to 0.52 g/L for surfactant
solutions of 20 mg/L at pH 6.0. The degradation effi- 60 40 ppm
ciency for various catalysts loading has been depicted 50
50 ppm
in Fig. 5. It can be observed that the photodegradation 40
efficiency increases with an increase in 0.10 mol % Fe- 30
doped ZnO–TiO2 concentration up to 0.2 g/L, and is 20
then decreased. This can be explained in terms of 10
availability of active sites on the catalyst surface and 0
the penetration of UV light into the suspension. The 0 60 120 180 240
total active surface area increases with increasing cat- Irradiation time, min
alyst weight. However, at the catalyst weight above Fig. 6. Effect of initial surfactant concentration. 10 mol %
optimum loading there is a decrease in UV light pene- Fe-doped ZnO–TiO2 0.2 g/L, 1 mM K2S2O8, pH 6, irra-
tration due to screening effect of excess catalyst parti- diation time, 4 h; Vt = 25 mL.

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 89 No. 13 2015

 SYNTHESIS AND CHARACTERIZATION of ZnO–TiO2 NANOPOWDERS
Degradation, %
100
90
80
70
60
50
40
30
20
10
0 6. R. Y. Hong, T. T. Pan, J. Z. Qian, and H. Z. Li, Chem.
0 1 2 3 4 5 6 7 8 9 10 11 12
pH
Fig. 7. Effect of pH on degradation efficiency. 20 mg/L
LABS, 0.2 g/L 10 mol % Fe-doped ZnO–TiO2, 1 mM
K2S2O8, irradiation time 4 h.
lysts. By increasing the intensity of light adsorbed by
molecules of surfactant, the excitation of photocatalyst
particles by photons will be reduced leading to diminish
in photodegradation efficiency [24].
Effect of pH
Photodegradation of surfactant was studied in a pH
range of 2.0–11 in the presence of 10 mol% Fe-doped
ZnO–TiO2 as catalyst (0.2 g/L) and K2S2O8 (1 mM).
The results for irradiation time of 5 h are shown in
Fig. 7. In all cases, the maximum degradation effi-
ciency was obtained in pH 6.0 for LABS. In presence
of 10 mol % Fe-doped ZnO–TiO2 and in pH 6.0, deg-
radation efficiency 94% is obtained. The interpreta-
tion of pH effects on the photocatalytic process is a
very difficult task because of its multiple roles such as
electrostatic interactions between the semiconductor
surface, solvent molecules, substrate and charged rad-
icals formed during the reaction process [25].
CONCLUSIONS
Therefore, we synthesized Fe-doped ZnO–TiO2
nanopowders for the first time using Pechini method.
The Pechini method is a promising alternative route or
mixed oxide powder preparation. The best photocata-
lyst in degrading LABS solution is 10 mol % Fe-doped
ZnO–TiO2. The optimal degradation conditions of
Linear Alkylbenzene sulfonate (LABS) are: 0.2 g/L
10% Fe-doped ZnO–TiO2, pH 6.0, 1 mM K2S2O8,
and concentration of LABS 20 mg/L. After 4 h irradi-
ation about 94% removal of LABS was achieved.
ACKNOWLEDGMENTS
The financial support provided by the Islamic Azad
University Lahijan is greatly acknowledged.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
2437
REFERENCES
1. S. H. Chiu and G. C. A. Huang, J. Non-Cryst. Solids
358, 2453 (2012).
2. R. Rajalakshmi and S. Angappane, Mater. Sci. Eng. B
178, 1068 (2013).
3. P. Hua, N. Hana, D. C. Zhanga, J. Hob, and Y. Chen,
Sens. Actuators B 169, 74 (2012).
4. N. C. Harihara, Appl. Catal. A 30, 455 (2006).
5. M. A. Behnajady, N. Modirshahla, and R. Hamzayi,
J. Hazard Mater. 133, 226 (2006).
Eng. J. 119, 71 (2006).
7. H. Gerisher and A. Heller, J. Electrochem. Soc. 139,
113 (1992).
8. U. G. Akpan and B. H. Hameed, Appl. Catal. A: Gen.
375, 1 (2010).
9. M. L. Zhang, T. C. An, X. H. Hu, C. Wang, G. Y. Sheng,
and J. M. Fu, Appl. Catal. A: Gen. 260, 215 (2004).
10. J. Wang, J. Wan, and K. Chen, Mater. Lett. 64, 2373
(2010).
11. X. H. Wu, Z. H. Jiang, H. L. Liu, X. D. Li, and X. J. Hu,
Mater. Chem. Phys. 80, 39 (2003).
12. D. E. Gu, B. C. Yang, and Y. D. Hu, Catal. Commun.
9, 1472 (2008).
13. Y. Li and J. P. Demopoulos, Hydrometallurgy 90, 26
(2008).
14. C. Shifu and C. Gengyu, Surf. Coat. Technol. 200,
3637 (2006).
15. M. I. B. Bernardia, L. E. Soledadea, I. A. Santosb,
E. R. Leitea, E. Longoa, and J. A. Varelac, Thin Solid
Films 405, 228 (2002).
16. H. Liu, J. Yang, Y. Zhang, L. Yang, M. Wei, and
X. Ding, J Phys.: Condens. Matter 21, 145803 (2009).
17. B. D. Cullity and S. R. Stock, Elements of X-ray Diffrac-
tion, 3rd ed. (Prentice-Hall, New Jersey, 2001).
18. L. Q. Jing, Z. L. Xu, X. J. Sun, J. Shang, and W. M. Cai,
Appl. Surf. Sci. 180, 308 (2001).
19. C. Lee and J. Yoon, J. Photobiol. A: Chem. 165, 35
(2004).
20. I. K. Konstantinous and T. A. Alabanis, Appl. Catal. B:
Environ. 49, 1 (2009).
21. J. Gimenz, D. Curco, and P. Marco, Water Sci. Tech-
nol. 35, 207 (1997).
22. C. J. da Silva and J. L. Faria, J. Photochem. Photobiol.
A: Chem. 155, 133 (2003).
23. J. M. Hermann, Catal. Today 53, 115 (1999).
24. B. Rohe, W. S. Veeman, and M. Tausch, Nano Tech-
nol. 17, 277 (2006).
25. U. G. Akpan and B. H. Hameed, J. Hazard. Mater.
170, 520 (2009).
Vol. 89 No. 13 2015