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Abstract
The present study is directed to clarify the influence of the ratio of anatase to rutile phase, containing in the TiO2 samples, on their activity
as photocatalysts in slurry. A series of samples corresponding to different percentages of anatase is prepared from commercial anatase and rutile
TiO2 brands (KRONOS). The crystalline phase composition of the samples is characterized by X-ray diffraction. The photocatalytic action of the
mixtures is tested in photodegradation of the commercial organic dyes Malachite Green Hydrochloride and Orange II in aqueous solutions under
UV irradiation. Comparative tests with Degussa P-25 are performed. The apparent rate constants of the process are determined from the kinetic
curves using appropriate models. They generally increase with the anatase ratio, being always larger for Malachite Green than for Orange II.
© 2007 Elsevier B.V. All rights reserved.
1. Introduction rutile and the anatase phases of TiO2 [13,14]. It has been compu-
tationally found that the anatase has a larger band gap (3.2 eV)
The present study is aimed to investigate the influence of than rutile (3.0 eV), although both of them have similar ground-
the anatase/rutile ratio in TiO2 powders, prepared from KRO- state properties [15]. It has been pointed out that in anatase,
NOS brands, on the photocatalytic oxidation of organics in the Fermi level is higher with about 0.1 eV than that of rutile
water solutions. Malachite Green Hydrochloride (MGH) and [16]. The photocatalytic efficiency of TiO2 depends also on the
Orange II (OII) are chosen as the model pollutants. The kinetics crystalline morphology and interfacial contact. The interplay
of photocatalysis of the composite powders is established and between these properties in titania, consisting of mixed rutile
compared to the photocatalytic behavior of commercial TiO2 and anatase, generally enhances the photocatalytic activity. For
Degussa P25. this reason the best commercial photocatalyst Degussa P25 con-
Commercial colorants, like MGH and OII [1–7], dissolved sist of anatase 80% and rutile 20% [14]. However, Degussa P25
in water have become a focus of the environmental remedia- is rather expensive (about 26 D kg−1 ) for large-scale applica-
tion efforts. A method, capable for waste-waters purification, tion in slurry for water remediation. For this reason attempts
especially at low dye concentrations, is the heterogeneous pho- are made to replace Degussa with a blend of other TiO2 brands,
tocatalysis in slurry. It comprises the UV-illumination of titania which can be better suitable in particular applications [7,9,12].
aqueous suspensions for the destruction of the dye onto the This is also our motivation in looking to utilize anatase and
surface of TiO2 particles [8–12]. Previously published works rutile of KRONOS TITAN GmbH Levercusen, Germany (ca.
on advanced oxidation technology claim that the photocat- 2.5 D kg−1 ).
alytic efficiency of TiO2 depends on its crystalline form. This In the allotropic forms, anatase and rutile, the coordination
variability has been attributed to differences in the rates of of Ti is sixfold with O atoms forming a distorted octahedron;
recombination, adsorptive affinity, or band gap between the the O atom is shared by three adjacent Ti atoms. The dis-
tortions of octahedra in these phases lead to crystallographic
differences and result in different arrangement of the Ti O and
∗ Corresponding author. Tel.: +359 2 8161 387; fax: +359 2 962 5438. Ti OH bonds on the surface of their particles. The titanium ions
E-mail address: nhtd@wmail.chem.uni-sofia.bg (C. Dushkin). in rutile and anatase are located on tetragonal sites, in which
0254-0584/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2007.05.035
188 A. Bojinova et al. / Materials Chemistry and Physics 106 (2007) 187–192
the two axial Ti O bonds are longer than the four equatorial
Ti O bonds [17]. The distortion of the TiO6 unit is greater
in anatase than in rutile. The structure of the most stable sur-
faces of TiO2 has been examined for the both modifications
[18]. The (1 0 1) surface of anatase and the (1 1 0) surface of
rutile exhibit twofold coordinate oxygen anions and fivefold Ti
cations, but the oxygen anions are more widely spaced on the
anatase surface. It is of interest to understand how the struc-
ture differences of TiO2 forms may affect the oxidative catalytic
processes.
As the first step, this investigation is focused on the influence
of the anatase and rutile content in the mixture on the photocat-
alytic oxidation of the organic dyes MGH and OII in aqueous
solutions. The results obtained from the composite samples by
variation of the anatase/rutile ratio are compared to those from
Degussa P25.
2. Experimental
2.1. Materials
The catalysts, used in the experiments are: Degussa P25 from Degussa
AG-Germany, anatase and rutile from KRONOS TITAN GmbH Levercusen,
Germany (referred to as KRONOS).
As model pollutants Malachite Green Hydrochloride (wavelength of
maximum absorbance λmax = 616 nm) from Sigma–Aldrich and Orange II
(λmax = 484 nm) from Fluka were used. The structural formulas of the organic
dyes are shown at Scheme 1.
The absorbance spectra of the dyes were determined by spectrophotometer
Jenway model 6400—see the insets to Fig. 1. In order to check the applicability
of the Lambert–Beer law for the dye in solutions, calibration lines were plotted
experimentally (Fig. 1).
Fig. 1. Calibration lines and change in the absorption intensity at the absorbance
maximum of the dyes Malachite Green Hydrochloride (a) and Orange II (b)
in water solutions. The insets represent the concentrations variations of the
absorbance spectra.
The composite samples were prepared from the commercial anatase and
rutile powders. The initial charge consists of a mixture of both allotropic forms,
precisely homogenized in glass mortar for 10 min. The composition of the sam-
ples corresponds to 25, 50, 60, 70, 75 and 80% anatase. A small quantity of
ethanol was used as mixing medium. The samples were thermally treated at
200 ◦ C for 2 h to assure complete removal of the ethanol and better contact
between the two phases.
The crystalline phase composition of the as-prepared catalysts was char-
acterized by X-ray analysis (Cu K␣ source radiation, diffractometer Siemens)
(Fig. 2).
The average crystallite size in the grains of Degussa P25 was calculated
from the peaks in Fig. 2a by the Scherrer equation to be 42 nm for the anatase
and 56 nm for the rutile phase. This is different from the literature data for the
average grain size obtained by TEM: 20–30 nm [7], 30 nm [19,20].
The X-ray diffractogramm in Fig. 2b illustrates smooth transition in the
intensity of the characteristic peaks for anatase and rutile, corresponding to the
change of the sample composition. In similar way, the average crystallite size for
KRONOS was calculated to be 40.7 nm for anatase and 40.9 nm for rutile [21].
The surface area of the dry powders, determined by BET analyses using N2
adsorption, is 57.6 m2 g−1 for Degussa P25. The literature data point 50 m2 g−1
[3,19,20], 44 m2 g−1 [4], 47 [7] and 48 m2 g−1 [22]. The respective values
Scheme 1. Structural formulas of Malachite Green Hydrochloride (a) and for TiO2 of KRONOS, measured by us, are 11.69 m2 g−1 for anatase and
Orange II (b). 11.57 m2 g−1 for rutile.
A. Bojinova et al. / Materials Chemistry and Physics 106 (2007) 187–192 189
Table 1
Sorption values of the organic dyes (initial concentration 10 ppm for MGH
and 20 ppm for OII, TiO2 loading 0.5 g l−1 ) reached at the sorption–desorption
equilibrium of the suspensions without UV-illumination
Catalyst Sorption (%)
MGH OII
Degussa P 25 9 20
Anatase 22 0
Anatase 80% 21 –
Anatase 75% – 3
Anatase 70% 19 –
Anatase 60% 20 2
Anatase 50% 24 –
Anatase 25% 23 5
Rutile 0 1
consists of multiphases of amorphous, anatase and rutile forms. P25 is of higher ability to destroy the organics than the mixture
The close proximity of these phases and in some cases the over- with respective composition. Nevertheless, the mixed KRONOS
lapping of forms makes it difficult to differentiate and it has been catalysts can be used in large-scale applications where important
documented to be the reason for long lasting excitation of elec- is the cost of material.
trons from the valence band to the conductive bands, allowing The influence of other factors, such as the synthesis tempera-
for efficient and effective degradation of organic compounds ture and the gas atmosphere of annealing, on the photocatalytic
[19,20]. Recently, Harum et al. had shown that in the case of properties of the mixed TiO2 powders will be object of short-
TiO2 P25 a transfer of the photogenerated electrons from rutile coming study [31].
to anatase particles takes place leading to stabilization of the
charge separation and therefore lowering the recombination of Acknowledgements
the photogenerated carriers, which determine the efficiency of
most photocatalysts. Additionally the small size of the rutile This research is financially supported by NATO Project SfP
particles in this formulation and their close proximity to anatase 977986. The authors are also thankful to Prof. D. Mechandjiev
particles are crucial to enhancing the catalyst activity [14]. from the Institute of General and Inorganic Chemistry, Bulgarian
Degussa P25 represents the most active commercial catalyst, Academy of Sciences, for the BET analysis of the samples and
concerning the photodegradation of various pollutants, while to Dr. A. Apostolov from the Faculty of Chemistry, University
there are cases were the pure anatase appears to have better pho- of Sofia, for the X-ray spectra.
tocatalytic properties than Degussa P25 [27]. According to refs.
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