Hindawi Publishing Corporation

International Journal of Photoenergy

Volume 2012, Article ID 626759, 8 pages
doi:10.1155/2012/626759

Research Article
Photocatalytic Degradation of Organic Dyes under
Visible Light on N-Doped TiO2 Photocatalysts

Olga Sacco,1 Marco Stoller,2 Vincenzo Vaiano,1 Paolo Ciambelli,1 Angelo Chianese,2
and Diana Sannino1
1 Department of Industrial Engineering, University of Salerno, Via Ponte Don Melillo, Salerno, 84084 Fisciano, Italy
2 Department of Chemical Engineering, University of Rome “La Sapienza”, Via Eudossiana 18, 00184 Rome, Italy

Correspondence should be addressed to Diana Sannino, [email protected]

Received 4 August 2012; Revised 5 September 2012; Accepted 12 September 2012

Academic Editor: Jiaguo Yu

Copyright © 2012 Olga Sacco 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.

This study was focused on the application of white and blue light emitting diodes (LEDs) as sources for the photocatalytic
degradation of organic dyes in liquid phase with visible light. The photocatalytic activity of N-doped titanium dioxide, synthesized
by direct hydrolysis of titanium tetraisopropoxide with ammonia, was evaluated by means of a batch photoreactor. The bandgap
energy of titanium dioxide was moved in the visible range from 3.3 eV to 2.5 eV. The visible light responsive photocatalysts showed
remarkably effective activity in decolorization process and in the removal of total organic carbon. Methylene blue was also used as
a model dye to study the influence of several parameters such as catalyst weight and initial concentration. The effect of dye on the
photocatalytic performance was verified with methyl orange (MO). The results demonstrated that the right selection of operating
conditions allows to effectively degrade different dyes with the N-doped TiO2 photocatalysts irradiated with visible light emitted
by LEDs.

1. Introduction photocatalytic efficiency. Furthermore, the typical prepara-

tion of transition metal-doped TiO2 requires more expensive
In recent years, an enormous interest has been devoted to ion-implantation facilities [26, 27].
heterogeneous photocatalysis using oxide semiconductors Recently, many efforts have been made to modify tita-
owing to its potential applications to both environmental nium dioxide with nonmetals, such as B, C, N, S, and F,
applications and organic synthesis [1–17]. Titanium dioxide, to efficiently extend the photoresponse from the UV to the
TiO2 , is characterized by chemical stability, no toxicity visible light region [28–40]. Furthermore, some theoretical
and cheap production cost, so that it represents one of calculations have also been performed to suggest that anion
the most important oxides employed in several fields of doping of TiO2 has considerable effects on the band gap
photochemistry, for example, in environmental remediation, alteration. Since the first report by Kobayakawa et al. [41],
photoelectrolysis of water and dye-sensitized solar cells considerable research has been done with respect to the
[18–22]. Since TiO2 absorbs only a small fraction of the preparation, characterization, photocatalytic activity, and
solar spectrum emission, due to the value of its bandgap mechanism of nitrogen-doped TiO2 in visible light. The
energy (3.0–3.3 eV), the metal-doped TiO2 has attracted N-doped TiO2 seems to be the most promising among
considerable attention due to its reported activity in the the so-called second generation photocatalysts. N-doping
visible light. Various metals such as Fe, Cr, Co, Mo, and can be obtained by various methods such as sputtering
V have been employed to tune the electronic structure and [42], treating of TiO2 powders in ammonia atmosphere
enhance the photocatalytic activity of titanium dioxide [23– [43], or hydrolysis with urea in the presence of organic
25]. However, metal doping can result in thermal instability or inorganic titanium-based compounds [44]. N-doped
and increase of carriers trapping, which may decrease the titanium dioxide nanoparticles (N-TiO2 ) demonstrated the
2 International Journal of Photoenergy

ability to degradate using tungsten bulb lamp [45] also

industrial wastewaters as tannery wastewater, which instead Air in Gas out
requires a complex combination of conventional treatments
to be satisfactory depolluted, as reported in [46].
Until now, there are very few reports on the use of LEDs
emitting in visible region for the degradation of methylene
blue, typically performed at very low dye concentration
(≤1 ppm) [47].
For the above reasons the objective of this study was
Led strip
to explore the possibility of using this type of LEDs as
source of visible light for the photocatalytic degradation
of dyes with higher concentration in the presence of N-
doped TiO2 photocatalyst. The catalyst was obtained by
direct nitration with NH3 during the hydrolysis of titanium
tetraisopropoxide. The influence of several parameters, such
as catalyst weight, methylene blue concentration, and dye
type were investigated.
300 400 500 600 700 800
Wavelength (nm)
2. Experimental Figure 1: Emission spectrum of the light sources and schematic
2.1. Photocatalysts Preparation and Characterization. N- picture of the photoreactor.
doped TiO2 photocatalysts were prepared by sol-gel method,
according to the modified synthetic procedure developed
by Sato [47]. Different amounts (25 mL, 50 mL, 75 mL, and performed with a pyrex cylindrical photoreactor (ID =
100 mL) of ammonia aqueous solution at 30 wt%, supplied 2.5 cm) equipped with an air distributor device (Qair =
by Carlo Erba, were added quickly to 25 mL of 97 wt% 150 cm3 /min (STP)), a magnetic stirrer to maintain the
titanium tetraisopropoxide (TTIP by Sigma Aldrich) at 0◦ C, photocatalyst suspended in the aqueous solution, and a
while the solution was vigorously stirred, leading to the temperature controller. The photoreactor was irradiated by
formation of a white precipitate. The precipitate was carefully a strip composed by 30 white light LEDs (nominal power:
washed with water and centrifuged to be separated. Finally, 6 W) with wavelength emission in the range 400–800 nm or
the obtained powder was dried and calcined at 450◦ C for 30 by a similar number of blue light LEDs (nominal power: 6 W)
minutes to get TiO2 in the anatase phase. X-ray diffraction with wavelength emission in the range 400–550 nm. The
(XRD) measurements of the obtained yellow samples were LEDs strip was positioned around the reactor so that the light
carried out with an X-ray microdiffractometer Rigaku D- source uniformly illuminated the reaction volume. The curve
max-RAPID, with Cu-Kα radiation. Laser Raman spectra inside Figure 1 represents the emission spectrum of white
were obtained at room temperature with a Dispersive Micro- LEDs, while the fraction of curve coloured in blue evidence
Raman (Invia, Renishaw), equipped with 785 nm diode- the spectrum emission of blue LEDs. On the left side of the
laser, in the range 100–2500 cm−1 Raman shift. Aggregates same figure a schematic picture of the photocatalytic reactor
sizes of photocatalyst particles in aqueous suspension were is presented. Slurry samples were collected at fixed time
measured by a DLS instrument (Brookhaven Plus 91). intervals, and centrifuged for 20 minutes at 4000 rpm for
UV-Vis DRS measurements were obtained by means of a removing photocatalyst particles. The centrifuged samples
Perkin Elmer spectrometer Lambda 35 using a RSA-PE-20 were analysed to determine the change of dyes concentration,
reflectance spectroscopy accessory (Labsphere Inc., North measured with a Perkin Elmer UV-Vis spectrophotometer
Sutton, NH). All spectra were obtained using an 8◦ sample at λ = 663 nm. A standard calibration curve was obtained
positioning holder, giving total reflectance relative to a cali- for different MB concentration and allowed to convert
brated standard SRS-010-99 (Labsphere Inc., North Sutton, absorbance to concentration (mg/L) units. Total organic
NH). The reflectance data were reported as the F(R∞ ) value carbon (TOC) of solution was evaluated from CO2 obtained
from Kubelka-Munk theory versus the wavelength. Band gap by catalytic combustion at T = 680◦ C. CO2 produced in gas-
determinations were made by plotting [F(R∞ ) ∗ hν]2 versus phase was monitored by continuous analyzers, measuring
hν (eV) and calculating the x intercept of a line passing CO, CO2 (Uras 14, ABB), and O2 (Magnos 106, ABB)
through 0.5 < F(R∞ ) < 0.8. gaseous concentrations.

2.2. Photocatalytic Activity Tests under Visible Light. In a 3. Results and Discussion
typical activity test a defined amount of photocatalyst was
suspended in 100 mL of MB solution. The suspension was The list of catalysts and their bandgap energy is reported in
left in dark condition for 2 hours to reach the adsorption Table 1.
equilibrium, and then photocatalytic reaction was initi- The reflectance measurements of N-doped TiO2 showed
ated under visible light up to 3 h. The experiments were that the absorption onset shifted from 380 to 480 nm
International Journal of Photoenergy 3

Table 1: List of catalysts and their bandgap.

NH3 solution
Catalysts TTIP volume Crystallites Aggregates Bandgap
volume (mL) N/Ti molar ratio SSA3 (m2 /g)
(mL) size2 (nm) size4 (nm) energy5 (eV)

TiO2 1 25 0 — 7 171 267 3.3

N1 25 25 4.6 16 75 163 2.6
N2 25 50 9.3 15 80 364 2.6
N3 25 75 13.9 16 75 167 2.5
N4 25 100 18.6 15 80 367 2.5
1
TiO2 by sol-gel method.
2 From XRD analysis.
3 From the equation SSA = 6000 ∗ (ρ ∗ d)−1 , where SSA is the calculated specific surface area, d is crystallites size (nm) and ρ is TiO2 density (g/cm3 ), based
on the assumption of spherical and nonporous particles [48].
4 From DLS instrument.
5 From UV-Vis spectra.

8
N 4
N 3
6
N 2
(F(R)∗hA)2

N 1
4 Undoped TiO2

Counts (a.u.)
2

0
2 2.2 2.4 2.6 2.8 3 3.2 3.4
hA (eV)

Figure 2: Bandgap estimation from UV-Vis DRS.

determining a decrease of bandgap values from 3.3 eV (the 100 200 300 400 500 600 700 800
typical bandgap of undoped TiO2 ) to 2.5 eV (Figure 2), Raman shift (cm−1 )
which is an unexpected value for the only anatase phase. This N 1 N 4
change in bandgap is therefore attributed to the presence of N 2 Undoped TiO2
nitrogen in the crystal structure phase. This result confirms N 3
the ability of photocatalysts to absorb visible light.
XRD analysis (not reported) revealed that for undoped Figure 3: Raman spectra of undoped TiO2 , N 1; N .2; N 3; N 4.
TiO2 and for N-TiO2 samples the only crystalline phase
is anatase and it did not change after the doping process.
The average size of TiO2 crystallites was calculated using The behaviour of MB decolourisation under visible light
the Scherrer equation [49] on diffraction plane (101) and generated by white LEDs is represented in (Figure 4) for
the obtained values are reported in Table 1. The crystallite undoped TiO2 and doped TiO2 with different nitrogen
average size was 16 nm for N 1 and N 3 samples, while for content.
N 2 and N 4 it was 15 nm. In contrast, DLS overestimated In dark conditions a decrease of MB concentration
the size of TiO2 particles due to agglomeration in the was observed during the first hour of the test and it was
suspension. For N-TiO2 samples, the degree of aggregation unchanged in the second hour, indicating that the adsorption
increased with decrease in crystallites size due to the high equilibrium of dye on catalyst surface was reached. The
surface energy of smaller particles. curves show that N-TiO2 catalysts have different amounts of
The results obtained from XRD are confirmed by Raman MB adsorbed in dark. To explain this last result, the specific
spectra (Figure 3), since the band positions are in complete area was estimated (Table 1); for the sample N 1 and N 3
accordance with those reported in previous studies for it was 75 m2 /g, while for N 2 and N 4 it was 80 m2 /g. As
anatase powder [50–61]. In fact the Raman modes at 141, expected, the amount of organic dye adsorbed increases the
194, 394, 515, and 636 cm−1 are assigned to the anatase higher is the specific surface area, fairly accordingly to the
phase. differences in the area values, as shown in Figure 4.
4 International Journal of Photoenergy

1.2
Dark
mineralized (2). For long reaction times also LMB can be
Visible light on
adsorption further degradated and mineralized.
1 The analysis of gases coming from the photoreactor
showed the presence of CO2 and SO2 during the visible light
0.8
irradiation, confirming the occurrence of MB mineralization
(Figure 5). In fact, a significant TOC reduction was obtained.
Its final value increased up to 97% by increasing the doping
0.6
C/C0

level (Figure 6). In this case, the order of activity was: N 4 >
N 3 > N 2 N 1.
0.4 The photocatalyzed decolorization process can be
described by a first-order kinetic equation (6) with respect
0.2 to the concentration of MB [62, 63]. Consider
C
− ln = ki · t, (6)
0 C0∗
0 100 200 300 400 500
Run time (min) where:
N 4 N 1
C = concentration of MB at any given time;
N 3 Undoped TiO2 C0∗ = concentration of MB after dark adsorption:
N 2 Photolysis t = irradiation time;
ki = apparent kinetic constant.
Figure 4: Decolorization of MB under visible light generated The obtained results are plotted in Figure 7.
by white LEDs; catalyst weight: 0.3 g; initial MB concentration: The order of kinetic constants of N-doped TiO2 after
7.5 ppm.
150 min of light irradiation is k2 > k4 > k3 ∼ k1 .
Many reports suggest that the amount of catalyst plays
a major role in the degradation of organic compounds or
After the dark period, the solution was irradiated with dyes in photocatalytic systems. To avoid the use of a catalyst
visible light and the reaction started to occur. Figure 4 excess, it is necessary to identify the optimum loading for
shows that undoped TiO2 is slightly effective for MB an efficient removal of dye or organic compound. So it is
decolourization, the C/C0 reduction being about 8%, a necessary to optimize the amount of catalyst with respect to
value similar to that of photolysis reaction (7%). On the the highest photocatalytic activity.
contrary, all the N-doped TiO2 photocatalysts exhibited To study the effect of the amount of catalysts, different
higher photocatalytic activity under visible light irradiation. quantities of powder between 0.05 and 1.5 g were used.
The order of decolorization activity of N-doped TiO2 after The initial concentration of MB dye (7.5 ppm) was kept
180 min was as following: N 2 > N 4 > N 3 ∼ N 1. The final the same in all these experiments. Figure 8 shows the effect
value of MB conversion depends on dye concentration after of the amount of catalyst on the conversion of MB in the
the dark period. presence of white LEDs. The progress of the conversion
The decolourization of MB does not necessary corre- is linear up to 0.3 g, while for further increase of catalyst
spond to the oxidation and mineralization of the molecule; in amount, the conversion stabilizes. These data indicate that
fact the reduced form of MB (LMB, leuco) which is colourless 0.3 g of powders are completely exposed to the radiation.
can be produced in the presence of light [49]. The lack of This phenomenon may be explained considering that with
coincidence among the best performing samples with respect an increase of catalyst loading in the aqueous medium, the
to either decolorization or mineralization can be the result of light penetration through the solution becomes difficult.
different routes followed by MB during irradiation. Consider Therefore 0.3 g of photocatalyst loading is considered to be
the following: an optimal value.
Also the dye concentration plays a key role in the photo-
h+ + OH− −→ OH• (1) catalytic degradation. The effect of MB initial concentration
on the photocatalytic activity was checked in the range
MB + OH• −→ INTERMEDIATES −→ CO2 (2) between 4 and 95 ppm with N 4 catalyst and optimal catalyst
loading (0.3 g in 100 mL of solution). The trend of the curves
−
MB + e− −→ MB• (3) was similar and it is shown in Figure 9. After 120 minutes
−
of dark adsorption, the photocatalytic test started. At fixed
2MB• −→ MB + LMB (4) reaction times, the increase of MB initial concentration
determined a decrease of the photocatalytic activity. This
LMB + OH• −→ INTERMEDIATES −→ CO2 (5) could be due to the increase of colour intensity of the
solution that reduces the light penetration into the aqueous
The MB molecule can be transformed into LMB through medium, meaning that the path length of photons inside the
reduction by electrons in the conduction band (4) or solution decreases. After 180 minutes of irradiation the final
oxidized by interactions with the valence band holes or native value of the decolorization was 100% in the case of 4 ppm
OH species, starting with a de-methylation step to be finally and 15% in the case of 95 ppm MB initial concentration.
International Journal of Photoenergy 5

Light on Light off

SO2

SO2 , CO 2 concentration (a.u.)

CO2

N
+ CH3
H3 C N S N
Cl−
CH3 CH3

0 25 50 75 100 125 150 175

Run time (min)

Figure 5: Gas analysis phase during visible irradiation of MB solution.

100 2.5
y = 0.0065x
R2 = 0.9944
80 2
y = 0.0109x
TOC removal (%)

R2 = 0.9874
60 1.5
−ln(C/C0 )

y = 0.0059x
R2 = 0.9913
40 1 y = 0.008x
R2 = 0.9905
20 0.5

0 0
TiO2 N 1 N 2 N 3 N 4 0 50 100 150 200
Irradiation time (min)
Figure 6: TOC removal after 180 min of irradiation time; catalyst
N 1 N 3
weight: 0.3 g; initial MB concentration: 7.5 ppm. N 4
N 2

Figure 7: Evaluation of decolorization kinetic.

The same effect was observed by Matthews during the
photocatalytic degradation of MB with TiO2 catalysts [48].
Moreover, the efficiency of the system was also evaluated one obtained with fresh catalyst because, using the same
with blue LEDs as source of visible light and methyl orange catalyst coming from the first test, a certain quantity of dye
(MO) as organic dye. Figure 10 shows the comparison is already adsorbed. The rate of dye removal depends on the
between the obtained results in presence of white and blue initial concentration in solution, so it is higher, the higher
LEDs. As expected from the evaluation of N 4 bandgap is residual MB after dark adsorption. However, it must be
energy (2.5 eV), only a fraction of radiation is used in the noted that the photocatalytic activity remained high and
decolorization process. In fact, the curves related to the the level of final MB removal was the same at the end of
MB concentration during the irradiation time showed a the test, indicating that no deactivation occurred and the
similar trend because the range of radiation used by the dye concentration decreased continuously under visible light
photocatalyst was that one having an emission wavelength irradiation.
lower than 440 nm. Similar results were obtained for methyl
orange (MO). 4. Conclusions
The photocatalytic stability of N-doped TiO2 was eval-
uated with recycling experiments (Figure 11). In the first In this study, the evaluation of the photodegradation of
cycle, the amount of MB adsorbed was lower than that methylene blue (MB), as dye model system, in presence of
6 International Journal of Photoenergy

30 1.2
Dark adsorption
1
25
0.8
MB conversion (%)

20

C/C0
0.6
15
0.4

10 0.2 Visible light on

5 0
0 50 100 150 200 250 300 350
Run time (min)
0
0 0.5 1 1.5 2 White LED MB Blue LED MB
Catalyst weight (g) White LED MO Blue LED MO
Figure 8: Evaluation of decolorization after 30 minute with Figure 10: Evaluation of decolorization with different dyes and
different amount of N 4 catalyst. different light source; initial MB and MO concentration: 9 ppm.

1.2 1.2
Dark
adsorption Visible light on Dark adsorption
1
1
0.8
0.8
C/C0

0.6

0.6 0.4
C/C0

0.2
0.4 Visible light on
0
0 50 100 150 200 250 300
0.2 Run time (min)
First recycle
Fresh
0
0 100 200 300 400 500 Figure 11: Evaluation of decolorization performances obtained
Run time (min) on N 4 photocatalyst after one recycling experiment; initial MB
4 ppm 16 ppm concentration: 7.5 ppm.
9 ppm 95 ppm

Figure 9: Evaluation of decolorization with different initial concen-

tration of MB; catalyst: N 4. carriers,” Photochemical and Photobiological Sciences, vol. 10,
no. 3, pp. 414–418, 2009.
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