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Materials Chemistry and Physics 106 (2007) 187–192

Anatase/rutile TiO2 composites: Influence of the mixing ratio on the


photocatalytic degradation of Malachite Green and Orange II in slurry
A. Bojinova a , R. Kralchevska a , I. Poulios b , C. Dushkin a,∗
a Department of General and Inorganic Chemistry, Faculty of Chemistry, University of Sofia, Sofia 1164, Bulgaria
bLaboratory of Physical Chemistry, Department of Chemistry, Aristotle University, 54124 Thessaloniki, Greece
Received 9 September 2006; received in revised form 16 May 2007; accepted 20 May 2007

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.

Keywords: Titanium dioxide; Photodegradation; Organic dyes; Slurry; Water purification

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.

2.2. Sample preparation and characterization

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

MGH and OII are pollutants.

the two dyes would have different saturation of the adsorption


on the TiO2 , which will affect the photocatalytic degradation.
To eliminate this stage we let the suspension with the dye stay
without illumination for 30 min prior the photocatalysis (stirring
and bubbling are on). The results for the sorption are shown in
Table 1 as the ratio of the decrease in absorbance during the
dark period to the initial absorbance. As expected, the sorption
Fig. 2. Comparative XRD patterns of Degussa P25 (a) and the prepared mixed of MGH on various TiO2 blends is more significant than the
TiO2 samples (b).
sorption of OII. The only difference is for Degussa P25 which
might be due to different charging of the catalyst surface.
2.3. Photocatalytic testing The results from the photocatalytic degradation of both pollu-
tants are shown in Fig. 3. The zero irradiation time corresponds
The experiments were performed in a cylindrical glass reactor (length
14.5 cm, inner diameter 4 cm and outer diameter 7.2 cm) [23]. The source of to the end of sorption period (30 min stirring without any illumi-
radiation was OSRAM DULUX DL18/71 UV lamp (length 22.5 cm, diameter nation). In case of MGH (Fig. 3a) the best results are observed
3.8 cm), emitting mainly in the range of 350–400 nm. The lamp is placed in a with the pure anatase sample, followed by that of Degussa P25.
Pyrex tube axially into the reactor. The volume of the water suspensions of TiO2 The photocataytic behavior of our mixed samples expresses a
was 250 ml. The catalyst loading was 0.5 g l−1 . This concentration was chosen
tendency of increasing the photocatalytic activity with raising
to satisfy two requirements: first, to provide a diluted suspension with enough
transparency for penetration of the UV light in the liquid volume and second, the anatase content. As expected, the deviations are more sig-
to assure enough catalysts particles for reliable destruction of the pollutant dye. nificant in case of MGH as basic dye, due to its higher sorption
The initial dye concentrations in the TiO2 suspensions were 10 ppm MGH and onto the catalyst samples (Table 1). Also, MGH exhibits higher
20 ppm OII, respectively, chosen to absorb measurable amount of light. The sus- slopes meaning stronger degradation than OII dye.
pensions were first stirred in the dark for 30 min to reach equilibrium sorption
Degussa P25 is the best performer in the photodegradation of
of the dye. After that the UV illumination was started to carry out the photo-
catalysis. Aliquot samples of 6 ml were taken at determined time intervals (at OII (Fig. 3b). This fact can be explained with its higher initial
lamp switched of) and filtered through 0.22 ␮m membrane filters to remove the sorption on TiO2 in this case (Table 1). Similar tendency can be
TiO2 particles. The change in the dye concentration in each aliquot was then observed for the composite samples—the photodegradation of
determined spectrophotometrically at the maximum of absorbance. pH was also OII is more effective with raising the anatase content. As seen
determined for each aliquot tested. The dye degradation was carried out at pH
from the data presented in Fig. 3, the deviations in case of OII
4.6–6 for MGH and pH 5.5–4.8 for OII. The temperature was 23 ± 2 ◦ C during
the experiments. are minimal (like for typical acid dye with much lower sorption
Stirring of and air bubbling in the suspension were kept constant along the on TiO2 than MGH).
experiments to assure oxygen saturation, uniform illumination of TiO2 particles From the presented data one can see, that the performance of
by UV light and constant transfer rate of the pollutants to the catalyst. the anatase allotropic form of KRONOS is always comparable
Blank experiments with the pure dye solutions, illuminated with UV light
to that of Degussa P 25.
for 2 h, were conducted prior the photocatalytic experiments. No significant
decolorization of the solutions was observed indicating that the direct photolysis To quantify the observed trends in Fig. 3, we first compared
of MGH and OII is negligible. the experimental data with a single exponential equation [24]:

C(t) = C0 exp(−kt) (1)


3. Results and discussion
Here C(t) is the actual dye concentration, while C0 is the ini-
MGH is a cationic dye with expected pronounced sorption tial dye concentration (at the end of sorption period); k has the
on the suspended TiO2 particles [4]. In contrast, OII is represen- meaning of apparent rate constant related to the adsorption and
tative acid azo dye with low level of sorption. For this reason, reaction properties of the solute in the frames of the Langmuir
190 A. Bojinova et al. / Materials Chemistry and Physics 106 (2007) 187–192

used in calculating the rate constants k, in order to minimize


variations as a result of the competitive effects of the interme-
diates, pH changes, etc. It is well known that the intermediate
products formed during photodegradation furthermore undergo
photocatalytic oxidation, while the simultaneous release of H+
influences the pH of the solution, thus resulting in a change of
the initial conditions [25].
Let us try to analyze now the complete set of experimental
data plotted in Fig. 3 up to the end of the process (40 min).
In many cases they deviate from the simple picture of single-
exponential decay described by Eq. (1). The most pronounced
deviations are observed with pure anatase in MGH solution and
with P25 in OII solution. To combat this problem we utilized a
more sophisticated model of double exponential equation [26]:
    
t t
C(t) = C0 (1 − B) exp − + B exp − (2)
τA τR

It considers the entire photocatalytic process as composed of two


stages: (i) adsorption of the dye, modeled as reversible chemical
reaction of first order and (ii) degradation of the dye expressed
as irreversible chemical reaction of first order. This is a simpli-
fication taking into account the transportation of the organics
from the solution volume to the TiO2 surface and next destruc-
tion of the absorbed molecules. Due to the appreciable sorption
(in Table 1) and the pronounced degradation ability (nearly 80%
of pollutant from Fig. 3a), the two processes are of comparable
rates at least in the case of pure anatase.
Fig. 3. Kinetics of water photopurification from the pollutants MGH (a) and The quantity τ A has the meaning of characteristic time of
OII (b) with the different catalyst samples. The experimental data points are the adsorption, which is kept constant equal to 1.25 min during the
average from two or three independent measurements; the error bars represent data fits for both dyes. According to the model proposed in
the respective deviations. The solid lines are theoretical fits of the data with Eq. deriving Eq. (2), τ A should be determined by studying the dark
(2).
sorption kinetics over the catalyst. However our experimental
data during the dark period are insufficient to perform such a
model at 1  k1 C (k1 is the adsorption constant) [24]. The appar- fit. That is why the two time constants, τ A and τ R have been
ent rate constants for the experiments with the different TiO2 determined simultaneously assuming that in some experiments
samples are plotted in Fig. 4. The k values are independently the dye adsorption is appreciable also during the photocatalysis.
obtained by a linear fit of the quantity ln(C/C0 ). Only the exper- The characteristic time of photocatalysis (reaction) τ R is var-
imental data obtained during the first 10 min illumination are ied between ca. 9 and 333 min for MGH and between 16 and
1000 min for OII. For comparison, in Fig. 4 we have plotted the
quantity 1/τ R ∼ k. It is seen, that they are rather close to the val-
ues for k obtained by Eq. (1). Regarding the matching constant
B, in many cases it has a value close to unity (0.9–1). The case
B = 1 transfers Eq. (2) into Eq. (1)—prevailing photocatalysis.
However, B = 0.6 in the case of pure anatase and MGH, which
shows appreciable contribution from the adsorption of dye.
As seen, the rate constant, k or 1/τ R , is always increasing
with the anatase content. Also, the rate constants in the case of
MGH are appreciably higher than those for OII, which means
more efficient MGH-dye degradation. This is due to the higher
sorption ability of MGH.
Finally, the data for Degussa P25 lay always higher than
Fig. 4. Influence of the anatase percentage in the TiO2 mixture on the rate those for the mixtures with similar anatase content. The supe-
constants, k, obtained from linear fits of the respective logarithmic plots of the
riority of TiO2 P25 may be attributed to the morphology of
experimental data up to the tenth minute (open figures). The rate constant values
for Degussa P25 are presented as asterisk (in case of MGH) and cross (in case crystallites, which was proposed to be one of the most criti-
of OII). The closed figures present the results for the reverse characteristic time, cal properties for the photocatalytic efficiency of P25 among
τ R , of the photodegradation process (in min−1 ). various grades of TiO2 . Crystallographic studies show that it
A. Bojinova et al. / Materials Chemistry and Physics 106 (2007) 187–192 191

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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