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Research Article
Photocatalytic Degradation of Methylene Blue
Using TiO2 Impregnated Diatomite
Correspondence should be addressed to Gaoxiang Du; dgx@cugb.edu.cn and Zhaohui Li; li@uwp.edu
Copyright 2014 Ranfang Zuo et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Nano-TiO2 showed a good catalytic activity, but it is easy to agglomerate, resulting in the reduction or even complete loss of
photocatalytic activity. The dispersion of TiO2 particles on porous materials was a potential solution to this problem. Diatomite
has high specific surface and absorbability because of its particular shell structure. Thus, TiO2 /diatomite composite, prepared by
loading TiO2 on the surface of diatomite, was a good photocatalyst, through absorbing organic compounds with diatomite and
degrading them with TiO2 . Scanning electron microscopy (SEM), energy dispersive spectrum (EDS), X-ray diffraction (XRD),
chemical analysis, and Fourier transform infrared spectrometry (FTIR) indicated that TiO2 was impregnated well on the surface of
diatomite. Furthermore, TiO2 /diatomite was more active than nano-TiO2 for the degradation of methylene blue (MB) in solution.
MB at concentrations of 15 and 35 ppm can be completely degraded in 20 and 40 min, respectively.
10 m2 /g. Its SiO2 content was 87%, with other elements, such [10]. The band at 797 cm1 was assigned to the symmetric
as Al, Fe, Ca, K, Mg, and Na. Tetrabutyl titanate was obtained stretching vibration modes of SiO bond and the strong
from commercially available. absorption peak at 400600 cm1 was attributed to the
vibration mode of SiOTi and TiOTi bonds [11].
2.2. Preparation of TiO2 /Diatomite Composite. Tetrabutyl
titanate was dissolved by ethanol and the solution was 3.4. Adsorption of MB on Different Catalysts and Characteriza-
gradually added to diatomite. The mixture was stirred for tion of Photocatalytic Activity. TiO2 almost had no adsorp-
2 h by magnetic stirrers and then dried in the oven at 80 C. tion as well as no photocatalyst for MB and the adsorption of
Finally, the dried mixture was further heated to 550 C for TiO2 /diatomite on MB was much lower than pure diatomite
about 2 h, before it was cooled naturally. The specific surface for MB (Figure 4). The adsorption reached equilibrium after
of TiO2 /diatomite composite is 32 m2 /g. 30 min in dark. Under dark conditions, TiO2 /diatomite
composite removed more MB in comparison to TiO2 and
2.3. Characterization. The particle size of diatomite powder control, showing almost no activity as well as no photocatalyst
was measured by a laser particle analyzer Mastersizer 2000. for TiO2 and the control (Figure 5), agreeable to the results
The morphologies of pure diatomite and TiO2 /diatomite presented in Figure 4. In the presence of UV, the rate of
composite were examined by scanning electron microscopy MB degradation by TiO2 /diatomite composite was higher
(SEM). X-ray diffraction analysis was performed using than that by TiO2 , attributing to its high surface area
a D5000 Diffractometer (Siemens) with a Ni filter and and high adsorbability. The MB at concentrations 15 and
CuK ( = 1.54 A) radiation. The UV-Vis absorbance 35 ppm could be completely degraded after irradiating 20
spectra were recorded using Varian Cary 5000. BET surface and 40 min, respectively. The control had the lowest MB
area was determined at liquid nitrogen temperature (77.3 K) self-degradation under UV light. The photoactivity of TiO2
using QUADRASORB SI-MP. loaded on diatomite was evidently increased because the
high surface area of diatomite effectively concentrates MB
3. Result and Discussion around the deposited TiO2 and produces high concentrations
of organic compounds for the TiO2 photocatalysis. The
3.1. The Microstructure and EDS Analysis of Diatomite and diatomite might improve the thermal stability of TiO2 and the
TiO2 /Diatomite Composite. Diatomite has porous structure surface area and preserve a higher content of surface hydroxyl
and rough surface after acid treatment (Figure 1(a)). The pore groups [12].
size of diatomite is between 2 and 5 m. After impregnation,
TiO2 particles formed a dense coating on the surface of 3.5. UV-Vis Absorption Analysis of MB Solution. Two major
the orifice, which presents honeycomb with smaller pore absorbance peaks of methylene blue were located at 292 and
(Figure 1(b)). Compared with raw diatomite, Ti element 664 nm, due to benzene ring and heteropolyaromatic linkage
appeared in the EDS analysis of TiO2 /diatomite composite, (Figure 6). In addition, the aqueous solution of MB molecules
indicating that TiO2 was successfully coated on the surface exhibited a double-peak feature at 664 and 615 nm, which
of diatomite. This result corroborates the high TiO2 content correspond to monomers and dimers, respectively [13]. Upon
detected by EDS analysis. irradiation, the peak at 664 nm has a progressively blue shift
to shorter wavelength (Figure 6(b)) because of hypsochromic
3.2. Chemical Analysis and XRD Patterns. Chemical compo- effect [14, 15]. The absorbance of MB solution was about
sition analyses showed that the content of TiO2 increased 2.5 a.u. at time zero. In the presence of TiO2 the absorbance
from 0.15 to 8.71% after TiO2 impregnation (Table 1). The of MB remained the same after 30 min (Figure 6(a)), agreeing
result together with that from the EDS analysis indicates well with the results in Figure 5, while the absorbance
that TiO2 was coated on the surface of diatomite success- of MB decreased sharply after 30 min in the presence of
fully. The reflections of TiO2 were characteristics of anatase. TiO2 /diatomite composite, indicating that TiO2 /diatomite
Diatomite is made of amorphous SiO2 with only trace amount composite has good adsorbability (Figure 6(b)). The absorp-
of quartz. The XRD pattern of TiO2 /diatomite composite tion peak at 615 nm becomes higher than the peak at
revealed mixed phases of anatase TiO2 and amorphous SiO2 664 nm after 30 min, indicating that the degradation rate of
(Figure 2). The coating of diatomite particles by TiO2 does monomers is much higher than that of dimers [14]. Besides,
not cause any change in their peak positions and shapes a parallel decrease in intensities and slight blue shift of the
compared with the pure TiO2 and diatomite. The results of bands located at 664 nm also could be observed. These are
XRD analysis and chemical analysis were consistent with that caused by the N-demethylated degradation concomitantly
of SEM analysis totally. with the degradation of the phenothiazine [16], as shown
in Figure 6(a). And MB was degraded completely after
3.3. FTIR Analysis. The FTIR spectrum of TiO2 /diatomite irradiating 60 min and 20 min by TiO2 and TiO2 /diatomite
composite consists of the characteristic peaks of TiO2 and composite, respectively.
diatomite (Figure 3). The band at 1089 cm1 was assigned
to the asymmetric stretching vibration modes of SiOSi 3.6. Mechanism of TiO2 Activation with UV Light and Pho-
bond [8, 9] and the band at 1633 cm1 was attributed to tosensitized Oxidation for MB and Its Identification of Inter-
the stretching mode of OH bonds on the surface of TiO2 mediate Products. The electron and the hole are generated
Advances in Materials Science and Engineering 3
Au
Si
O
Ti
Ti
Al Au Ti
C
0 1 2 3 4 5
Energy (keV)
100 nm 100 nm
(a) (b)
2400 100
90
2000
80
1633
797
(c)
Transmittance (%)
1600 (c) 70
Intensity (a.u.)
1650 1650
60 (b)
797
463
1200
50
(a)
(b) 40
800
1089
463
30
400 20
(a)
10
1089
563
0
0
4500 4000 3500 3000 2500 2000 1500 1000 500 0
10 20 30 40 50 60 70
Wavenumbers (cm1 )
2 ( )
TiO2
TiO2 Anatase
Diatomite
Diatomite Quartz
TiO2 /diatomite
TiO2 /diatomite
Figure 3: FTIR spectra of TiO2 (a), diatomite (b), and TiO2 /diatom-
Figure 2: XRD patterns of TiO2 (a), diatomite (b), and TiO2 /dia-
ite composite (c).
tomite composite (c).
17
16
Concentration (mg/L)
15
14
13
12
11
10
0 30 60 90 120 150
Time (min)
Blanking Diatomite
TiO2 TiO2 /diatomite
16
35 UV light on
14 UV light on
30
12
25
Concentration (mg/L)
Concentration (mg/L)
10
20
8
15
6
Adsorption 10
4
Adsorption
2 5
0 0
2 5
40 20 0 20 40 60 80 100 40 20 0 20 40 60 80 100
Time (min) Time (min)
TiO2 TiO2
TiO2 /diatomite TiO2 /diatomite
Blanking Blanking
(a) (b)
Figure 5: Kinetics of photocatalytic MB degradation from initial MB concentrations of 15 (a) and 35 mg/L (b).
The hydroxyl radical existing on the surface of diatomite The typical HPLC chromatograms of MB degraded by
accelerated the degradation of MB (B3): TiO2 /diatomite under UV light were shown in Figure 7.
HPLC analyses showed no degradation products of MB
under the condition of adsorption (Figure 7(a)). The decrease
MB + TiO2 MB+ eCB (TiO2 ) (B1) in peak height was just caused by adsorption of MB on
TiO2 /diatomite (Figure 7(b)). However, the adsorption of
O2 + e O2 (B2)
the dye molecules over the TiO2 surface directly affects the
MB+ + OH MB + OH (B3) occurrence of electron transfer between the excited dye and
TiO2 which further accelerated the degradation rate [20]. In
MB+ + OH products (B4) the inserts, peak number 1 represented the retention time of
MB, peak number 2 was the self-degradation intermediate
MB+ + O2 products (B5) metabolite of MB, while peaks number 3 and 4 were further
Advances in Materials Science and Engineering 5
2.5 2.5
2.0 2.0
Absorbance (a.u.)
Absorbance (a.u.)
1.5 1.5
1.0 1.0
0.5 0.5
0.0 0.0
100 200 300 400 500 600 700 800 100 200 300 400 500 600 700 800
Wavelength (nm) Wavelength (nm)
0 min Irradiation, 40 min 0 min
Absorbance, 30 min Irradiation, 60 min Absorbance, 30 min
Irradiation, 20 min Irradiation, 20 min
(a) (b)
Figure 6: UV absorption spectra of MB solution after reacting with TiO2 (a) or TiO2 /diatomite composite (b) at different time.
20
200 1
15
4 3 2 1
10
160 5 1
2
0
5 2
120 2.5 3.0 3.5 4.0 4.5
Time (min)
(a)
1
80
2
40 (b)
(c)
0 (d)
0 1 2 3 4 5 6
Time (min)
Figure 7: HPLC analyses of MB. (a) Initial MB solution at 15 ppm, (b) equilibrium MB solution after 30 min absorption in the dark, (c) after
UV irradiation for 5 min, and (d) after irradiation for 20 min.
degradation products of MB (Figure 7(c)). Peaks number 3 double bond conjugation, which induces the opening of the
and 4 were further degraded to CO2 completely in addition central aromatic ring containing both heteroatoms, S and N.
to further reduction of peak height of peaks number 1 The origin of H atoms necessary to CH and NH bond
and 2 after UV irradiation for 20 min. These results are in formation can be proposed from the proton reduction by
agreement with the results shown in Figures 5 and 6(b). The photo-generated [21].
MB and its progressive degradation products corresponding
to the peaks of 1, 2, 3, and 4 were reported in Scheme 1.
The OH radicals can attack the CS+ =C functional group 4. Conclusion
in MB, which is in direct Coulombic interaction with the
surface of TiO2 /diatomite. Therefore, the initial step of MB Impregnation of diatomite with TiO2 yielded supported
degradation can be ascribed to the cleavage of the bonds anatase catalyst for MB photodegradation. The diatomite
of the CS+ =C functional group in MB. The passage from supported anatase catalysts were more active than the nano-
CS+ =C to CS(=O)C requires the conservation of the TiO2 , probably due to the adsorption of MB on diatomite
6 Advances in Materials Science and Engineering
N
1
H3 C N S
+ CH3
N
CH3
CH3
NH2
2
S N CH3
H3 C N
CH3
CH3 O NH2
NH2 4
H3 C N
H3 C N SO3 H
CH3
CH3
OH
3
H3 C N OH
CH3
CO2
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