Documente Academic
Documente Profesional
Documente Cultură
(2011) Photocatalytic
decomposition of Trypan Blue over nanocomposite thin films.
Kinetics and Catalysis, 52 (3). pp. 391-396. ISSN 0023-1584
Link to official URL (if available):
http://dx.doi.org/10.1134/s0023158411030037
The original publication is available at www.springerlink.com
Abstract
The photocatalytic activity of titanium dioxide (TiO2) and gold (Au) modified TiO2 (Au/TiO2), supported in
polymethylmethacrylate (PMMA) thin film, was evaluated in the photodegradation of Trypan Blue (TB) under sunlight
irradiation. The effect of parameters such as the photocatalyst amount and pH on TiO2 photocatalytic activity is investigated.
Oxygen flow stream was applied to enhance the decomposition process of TB. The maximum photoactivity was attained
using Au/TiO2-PMMA thin film at pH=2.
Keywords: TiO2, Au/TiO2, photocatalyst , Trypan Blue, PMMA &pH
1Introduction
was used efficiently as a catalyst for photocatalytic
degradation of azo dye Disperse Yellow 23 in water.
This study shows that pH is one of the main affecting
factors on the degradation of azo dye Disperse Yellow
23 [16]. TiO2 codoped with Fe3+ and Ho 3+ ions
(H2O
H+ + OH)ads + h+vb
H+ + OH;
R + OH
R + H2O,
+
+
R+h
R
degradation products
2.2.Polymersynthesis
PMMA polymer was prepared according to the free
radical polymerization process [23]. Methyl
methacrylate (99.0%, Fluka) was purified via
distillation under reduced pressure. About 100 ml
(density 0.943 g/mL ) of purified methyl methacrylate
monomer was taken in a Pyrex glass jar. Traces of
benzoyl peroxide were added to catalyze the radical
polymerization. The mixture was deoxygenized by
purging with argon. Oxygen may cause oxidative
degradation of macromolecules that have already been
formed [24]. The jar is then sealed and kept
undisturbed for 48 h at 55 C. The temperature is
raised gradually to 90 C for 5 h to get rid of the
remaining traces of unreacted initiator and monomer
by evaporation [25]. Before taking the samples out of
the oven, its temperature is decreased slowly to 25 C
over a period of 24 h.
2.3.PreparationofTiO2thinfilm:
First, 300 mg PMMA was dissolved in 10ml
tetrahydrofuran (Fluka). A proportional amount of
TiO2 (0.04,0.08g) powder was suspended in the
dissolved polymer.
The mixture was uniformly
distributed in a Pyrex glass Petri dish (100 mm in
diameter) and left to dry for 24h at room temperature.
Au/TiO2 thin film was prepared by the same method.
e e
e
e
h h
e
h
h
h h
TB
Au/TiO2embeddedintoPMMA
2.4.Preparationofgoldnanoparticles
gold nanoparticles was prepared by chemical
reduction of HAuCl4, according to Turkevichs
method [26], 95 mL of a chlorauric acid (HAuCl4)
solution containing 2.5 mg of Au is refluxed and 5 mL
of 1% sodium citrate solution is added to the boiling
solution. The solution is further boiled for 30 min and
is then left to cool to room temperature.
0 .4
0 .2
0 .0
4 00
50 0
6 00
700
8 00
W avelength(nm )
1cm.
absorbance(a.u.)
2Experimental
Chemicals: The P25 TiO2 (ca. 80% anatase, ca. 20%
rutile) supplied by Degussa, with a typical surface area
of 50 15 m2/g, average primary particle size 21 nm
and band gap 3.03 eV for rutile and 3.18 for anatase.
2.1.PreparationofAu/TiO2
50 ml aqueous solution contains 0.08 g TiO2 and 5 ml of
5x10-3 mol dm-3 HAuCl4 (Aldrich) was stirred whilst
heating until boiling. Then 1 ml of 0.5% of sodium
pH2/ TiO2PMMA
zero
Absorbance (a.u.)
0.8
A/A0
0.0
60
80
100
120
150 min.
140
160
IrradiationTime(min.)
Figure 3: Effect of different pHs on TB (1x10-5 mol dm,max=585nm) degradation efficiency using 0.08 g TiO2PMMA thin film and sunlight irradiance 500-600 W/m2.
600
700
800
pH2
pH4
pH6
pH8
pH2blankonPMMA
pH2blank
40
0.2
0.6
20
90
120
Wavelength (nm)
0.8
60
0.4
500
1.0
0.2
30
0.0
Effect of pHs:
TiO2-PMMA thin film was used to examine TB
photostability in neutral, acidic and basic media. The
pH of the sample is an important parameter in the
photodegradation taking place on semiconductor
particle surfaces, since it is related to the surface
charge properties of the photocatalyst. The pH of an
electrolyte can vary the surface charge of the
photocatalyst and also shifts the potential of some
redox reaction. Thus, it affects the adsorption of
organic solutes [29]. On the other hand, TiO2 surface
charge is zero at pH 6.3. This means that the TiO2
surface is positively charged (TiOH2+) when the pH
is lower than this value and negatively charged (TiO)
when the pH is higher than this value[30].
0.4
0.6
pH7/ TiO2PMMA
1.0
pH=2
1.0
0.8
0.8
blank
polymer
Tio0.04
Tio0.08
0.4
0.6
A/Ao
A/A0
0.6
0.4
0.2
Blank TB
Blank TB on PMMA
0.04 gm Tio2PMMA
0.08 gmTio2PMMA
Au/TiO2PMMA
0.2
0.0
0
20
40
60
80
100
120
140
160
zero
15
absorbance (a.u)
80
100
120
140
160
180
0.8
30
45
60
75
90
105 min.
0.2
60
pH2 Au/TiO2
0.4
40
Irradiation Time(min.)
0.6
20
0.0
500
600
700
800
Wavelength (nm)
Nanoparticle
Conc.
Blank (0 g)
TiO2 (0.04 g)
TiO2 (0.08 g)
Au/TiO2 (0.08 g)
Time
(min.)
150
150
150
105
Photodegradation
%=( Ao- At )x100
20
79
87
90
Photodegradation rate
Ao - At / t
2.2x10 -5 mol dm-3 sec-1
8.8x10 -5 mol dm-3 sec-1
9.7x10 -5 mol dm-3 sec-1
1.4x10 -4 mol dm-3 sec-1
Conclusions
Although TB is known for its high photostability. We
report a higher TB photodegradation rate using gold
deposited on TiO2 polymer film than using TiO2 alone
at the same pH value. In addition, the photocatalytic
degradation was effective in acidic environment, the
degradation of TB was at its greatest at acidic pH=2
while it was lowest at basic pH=8.
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