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Comparative Study on the Photocatalytic Degradation of Paraquat Using

Tungsten-Doped TiO2 Under UV and Sunlight

Chapter · January 2019

DOI: 10.1007/978-981-13-6717-5_15

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Comparative Study on the Photocatalytic
Degradation of Paraquat Using
Tungsten-Doped TiO2 Under UV
and Sunlight

Manpreet Kaur, Anoop Verma, Hema Setia and Amrit Pal Toor

Abstract Photocatalytic degradation of paraquat dichloride a poisonous dipyridil-

ium herbicide present as a pollutant in surface water has been studied in a batch pho-
toreactor using P25 TiO2 and tungsten (W)-doped TiO2 . Effect of varying parameters
such as substrate concentration, catalyst loading, pH of the solution, light conditions,
type of catalyst, and amount of dopant has also been studied. It was observed that
synthesized catalyst with 2.5 wt% W-doped TiO2 exhibited higher percentage degra-
dation efficiency than bare TiO2 under optimum conditions of catalyst loading, pH,
and substrate concentration under solar irradiation. W-TiO2 catalyst has been synthe-
sized and characterized using UV–Vis DRS, XRD, SEM-EDS, and TEM techniques.
Maximum degradation of 98% was observed for 25 ppm paraquat, at a pH of 6.5,
catalyst loading of 1 g L−1 , and 2.5 wt% W-doped TiO2 under sunlight.

Keywords Paraquat · Photocatalysis · Degradation · Doping · Tungsten-doped

TiO2 · Wastewater

1 Introduction

Herbicides are used to control, eliminate, or destroy pests in order to protect the food
crop. However, their extensive and exhaustive use over the past decade has posed a
threat to the environment. Due to their high toxicity and persistence, they have been
found to have adverse ecological impact on aquatic life and human health. Therefore,

M. Kaur
Energy Research Centre, Panjab University, Chandigarh 160014, India
A. Verma
School of Energy and Environment, Thapar Institute of Engineering and Technology, Patiala, India
H. Setia (B)
University Institute of Engineering and Technology, Panjab University, Chandigarh 160014, India
e-mail: hemasetia@pu.ac.in
A. P. Toor
Dr SSB University Institute of Chemical Engineering and Technology, Panjab University,
Chandigarh 160014, India
© Springer Nature Singapore Pte Ltd. 2019 145
A. K. Agnihotri et al. (eds.), Sustainable Engineering, Lecture Notes
in Civil Engineering 30, https://doi.org/10.1007/978-981-13-6717-5_15
146 M. Kaur et al.

it becomes imperative to assess the fate of such herbicides and develop a mechanism
for its removal and degradation in soil and waste bodies. Depending upon the envi-
ronmental conditions, herbicides can persist in many environmental compartments
for a long period of time. Starting from their point of application in field, these com-
pounds undergo different chemical and physical processes like adsorption on to soil
matrix, leaching into groundwater, and transport to surface runoff water. The differ-
ent strategies that can reduce the pesticides concentration involve direct photolysis,
wherein the degradation or transformation to other products takes place in the pres-
ence of sunlight. Advanced oxidation processes offer the advantages of destroying
such pollutants by oxidizing them into mineral salts and nontoxic compounds under
normal conditions of temperature and pressure.
Numerous research documents have demonstrated that heterogeneous photocatal-
ysis, a representative of advanced oxidation process, is an effective process for the
degradation of a variety of toxic substances, such as fungicides and herbicides, under
different light irradiations (Shibin et al. 2015; Verma et al. 2014; Kaur et al. 2016;
Grover et al. 2017). Recently, doping, co-doping, immobilization, impregnation, and
supported catalyst systems have been investigated to enhance the degradation of such
organic compounds (Cunff et al. 2015; Montañez et al. 2015; Maulidiyah et al. 2017;
Kalantaria et al. 2017; Sakee and Wanchanthuek 2017; Kruanetr and Wanchanthuek
2017; Moctezuma et al. 1999; Cantavenera et al. 2007). Zahedi et al. (2015) demon-
strated 84.39% degradation of 10 ppm paraquat in 5 h at pH 5.8 using N,S codoped
TiO2 thin films under visible irradiation. Eleburuike et al. (2016) achieved 80.798%
degradation of paraquat in 4 h with CeO2 -modified TiO2 nanotubes and catalyst
loading of 0.38 g under UV irradiation. Limited data is available on the degradation
of paraquat under visible illumination using surface-modified TiO2 . Surface modi-
fication of TiO2 with metal ions can significantly enhance its photocatalytic activity
under economical sunlight. Although photocatalytic degradation of paraquat using
titania under UV light has been widely studied, the aim of the present study is to
achieve higher degradation efficiencies using modified TiO2 under naturally available
solar illumination.

2 Methodology

2.1 Materials

All the chemicals procured were used as received without any further purification.
Paraquat was obtained from Sigma Aldrich (>99% pure, technical). Titanium dioxide
(P25) (purity 97%, average particle size-30 nm, 80% anatase) was procured from
Evonik India. Tungsten trioxide (WO3 ) was obtained from Central Drug House.
Distilled water was used throughout the experiment for preparing solutions. Millipore
membrane filters (0.22 μm) were used to filter the samples before analysis.
Comparative Study on the Photocatalytic Degradation … 147

Table 1 Crystallite size

Sample Crystallite size Bandgap energy
calculated from Scherrer’s
(nm) (eV)
equation
P25 TiO2 32.64 3.20
1.5 wt% W-TiO2 30.22 3.16
2.0 wt% W-TiO2 29.94 3.00
2.5 wt% W-TiO2 27.58 2.80
3.0 wt% W-TiO2 31.37 2.94

2.2 Synthesis of W-Doped TiO2 Nanoparticles

Tungsten-doped titanium dioxide (W-TiO2 ) was prepared by mechanical mixing

through homogenization and magnetic stirring. Aeroxide TiO2 P25 was used as the
precursor. Precisely, calculated amount of TiO2 was dispersed in 50 ml distilled water
under continuous stirring. Tungsten trioxide was taken as the source for doping TiO2 .
Appropriate concentrations of WO3 were then dispersed in 100 ml of distilled water
by continuous stirring for 30 min at room temperature. This solution was gradually
added to TiO2 solution under vigorous stirring to get a uniformly dispersed solution.
The sediments thus obtained were dried in an oven and calcined at 400 °C for 4 h.

3 Results and Discussion

3.1 Characterization of Catalyst

The X-ray diffraction patterns of TiO2 P 25 and 2.5 wt% W-doped TiO2 are illustrated
in Fig. 1. The anatase phase located at 2θ equal to 25.4°, 37.8°, 48.1°, and 55.2°
corresponds to (101), (004), (112), (200) and (211) planes, whereas peaks located at
2θ equal to 27.5°, 36.2°, 39.3°, 41.3°, and 54.4° corresponds to the rutile phase which
were also observed in W-TiO2 (Zahedi et al. 2015). Since the XRD pattern of W-
doped TiO2 does not show any major shift or distortion to the main characteristic peak
of TiO2 , we can say that doping of TiO2 with W does not change the basic crystalline
state of TiO2 . The results suggest that W was well dispersed on the surface of TiO2
particles. A small percentage of rutile phases were also observed in W-TiO2 as were
observed in P25 TiO2 suggesting that this method of doping with W does not favor
the anatase to rutile or rutile-to-anatase phase transition.
The crystalline size of W-doped TiO2 was calculated using the Scherrer’s equation
(Toor et al. 2013) and is listed in Table 1. The smallest crystallite size of the W-doped
TiO2 was 27.58 nm for 2.5 wt% W-doped TiO2 ; hence, the TEM analysis of this
sample was carried out.
148 M. Kaur et al.

Fig. 1 a XRD pattern of P25 TiO2 , b 2.5wt% W-TiO2

Fig. 2 TEM image of the 2.5 wt% W-TiO2 nanoparticles

The morphology of the synthesized 2.5 wt% W-doped TiO2 was characterized by
TEM, and the result is shown in Fig. 2. The particles of W-TiO2 are seen to be nearly
cubic in shape.
The elemental composition of the synthesized W-TiO2 was examined by energy-
dispersive spectroscopy. Figure 3 illustrates the EDS for 2.5 wt% W-doped TiO2.
EDS results confirmed the presence of 2.45 wt% tungsten element in the W-TiO2
sample, thus confirming the doping of tungsten over TiO2 .
Comparative Study on the Photocatalytic Degradation … 149

Fig. 3 SEM and EDS image of 2.5 wt% W-doped TiO2

To study the optical response difference of synthesized W-TiO2 catalyst, the

absorption spectra and diffuse reflectance spectra (DRS) analysis were performed
with a UV–Vis spectrophotometer (Fig. 4a). The UV–Vis absorption spectra were
measured in the wavelength range of 200–700 nm taking BaSO4 as reference com-
pound. Optical bandgap was calculated using the relation αhν = A (hν − Eg )n , where
α is the absorption coefficient and is calculated using Beer–Lambert relation: α =
2.303 A/t, A is the absorbance, t is the film thickness, h is the Plank’s constant, and
Eg is the optical bandgap energy (Baruwati et al. 2006). The value of exponent n
depends on the type of transition and can take values of 1/2, 2, 3/2, and 3 for allowed
direct, allowed indirect, forbidden direct, and forbidden indirect transitions, respec-
tively (Manjunatha and Paul 2015; Dhaouadi and Adhoum 2009; Zahedi et al. 2015).
The linear part of the plot of (αhν)2 versus hν (Fig. 4b) was extrapolated to obtain
the Eg values for the W-TiO2 catalyst with varying wt% of tungsten in TiO2 . The
values so obtained (Table 1) reveal that the bandgap energy for the doped particles
is smaller than those for the pure TiO2 . Further, the bandgap energy was observed
to be lowest at 2.8 eV for 2.5 wt% doped W-TiO2 . Low values of bandgap energy
enable the absorption of light in the visible region.

3.2 Degradation Studies

The irradiation experiments were performed in a UV chamber consisting of UV

fluorescent lamps (Philips, 20 W) having wavelength of 365 nm. The UV intensity
was measured and kept constant at 25 Wm−2 for the entire experimentation. Herbi-
cide solutions were prepared by dissolving appropriate amounts in distilled water.
Hemispherical-shaped shallow pond slurry reactor was used to carry out the batch
experiments. For each run, a 200 ml sample of the herbicide solution with varying
amount of catalyst was irradiated under UV or sunlight for 180 min. The concen-
tration of paraquat was determined using a UV–Vis spectrophotometer. The λmax
was observed at 257 nm (Moctezuma et al. 1999). Prior to irradiation, the solutions
were kept in dark for 30 min under stirring conditions for adsorption of the herbi-
150 M. Kaur et al.

Fig. 4 a Diffuse reflectance (a) 1.6

spectra of TiO2 (P25) and P25
synthesized W-TiO2 1.5 wt%
1.2
nanoparticles, b plot of 2 wt%

Absorbance (a.u)
(Ahν)2 versus hν for the 2.50%
W-TiO2 nanoparticles with 0.8 3 wt%
varying wt% of tungsten
0.4

-0.4
200 300 400 500 600 700
Wavelength (nm)

(b)
P 25 (3.2 eV)
60 1.5 wt% (3.16 eV)
2 wt% (3.0 eV)
2.5 wt% (2.8 eV)
3 wt% (2.94 eV)
40
(αhν)2 / (eV)2

20

0
2.5 3 3.5 4 4.5 5 5.5 6
Photon energy (eV)

cide on the surface of the catalyst. No significant photolytic and photodegradation of

paraquat was observed. Similar results have been observed by Florêncio et al. (2004)
and Cantavenera et al. (2007).

3.3 Effect of Catalyst Loading

To determine the minimum catalyst loading required for the optimum degradation
of paraquat, reactions were carried out by varying the TiO2 loading from 0.5 to 1.5 g
L−1 . The results demonstrate that photocatalytic activity increased linearly up to 96%
for a catalyst loading of 1 g L−1 (Fig. 5). However, the degradation started decreasing
with further increase in the amount of catalyst. This can be attributed to an increase
in the solution turbidity that blocks the penetration of light into the solution (Wei
and Wan 1991) also referred to as shielding effect. Similar studies on the complete
degradation of paraquat have been reported. For same catalyst loading, Florêncio
Comparative Study on the Photocatalytic Degradation … 151

110

Degradation (%)
90

70

50
0 0.5 1 1.5 2
Amount of TiO2 (g L-1)

Fig. 5 Effect of amount of P25-TiO2 on the photocatalytic degradation of paraquat (25 ppm, pH
6.5, UV irradiation for 3 h)

et al. (2004) have reported almost complete degradation for 7 ppm paraquat solution
at an intensity of 126 klx, whereas in this study a degradation of 96% was achieved
for 25 ppm paraquat at an intensity of 25 Wm−2 which is the intensity of UV available
in solar light (i.e., 3–4% of the solar irradiation).

3.4 Effect of Substrate Concentration

The effect of substrate concentration is an important parameter for studying the

degradation rate. The degradation of paraquat was studied for 25, 50, 75, and 100 ppm.
It was observed that as the concentration of the substrate is increased from 25 to
100 ppm the percentage degradation decreased from 96 to 51%. Lower substrate
concentrations were found to be favorable for photocatalytic degradation of paraquat.
At higher concentrations, the OH radicals produced are not sufficient to degrade the
substrate molecules which are absorbed on or near the catalyst surface (Fig. 6).

3.5 Effect of pH

Effect of pH is also an important parameter because it commands the surface charge

properties of the catalyst and therefore the adsorption of the substrate. The pH studies
in the range 4–11 were carried out for 25 ppm paraquat with catalyst amount of 1 g
L−1 under UV irradiation. A significant variation in the degradation of paraquat was
observed with change in the pH. The results depicted in Fig. 7 show that at pH 4 little
or negligible degradation of paraquat takes place. Paraquat is positively charged,
so low pH hinders the adsorption on the catalyst surface leading to the observed
low rates of degradation. While basic pH favors the degradation of paraquat, the
152 M. Kaur et al.

1
25ppm
50ppm
0.8
75ppm
100ppm
0.6
C/Co
0.4

0.2

0
0 30 60 90 120 150 180 210
Time (min)

Fig. 6 Effect of substrate concentration on the photocatalytic degradation of paraquat (P25 TiO2
1gL−1 , pH 6.5, UV irradiation)

Fig. 7 Effect of solution pH 1

on the photocatalytic
degradation of paraquat 0.8 pH 4
(25 ppm, TiO2 1gL−1 , UV
pH 6.5
irradiation) 0.6 pH 9
C/Co

pH 10
0.4 pH 11

0.2

0
0 50 100 150 200
Time (min)

maximum degradation of up to 96% was observed at the natural pH of aqueous

paraquat that is 6.5. Under alkaline conditions, the surface of the catalyst becomes
negatively charged which explains the enhanced adsorption and degradation of the
cationic paraquat molecule (Moctezuma et al. 1999; Shamsedini et al. 2017; Garcia
et al. 2017). Similar results have been reported for the photocatalytic degradation of
3,4-dichlorophenol at different pH (Toor et al. 2005).

3.6 Activity Comparison of TiO2 and Doped W-TiO2 Under

Solar Illumination

The activity of TiO2 and the synthesized W-doped TiO2 with varying weight per-
centages of W was studied under natural solar irradiation and optimized parameters
of catalyst loading, substrate concentration, and solution pH. The experiments were
carried out on sunny days in clear skies with average solar intensity of 430 klx. A
comparison of the solar photocatalytic degradation of paraquat with TiO2 and vary-
Comparative Study on the Photocatalytic Degradation … 153

Fig. 8 Solar photocatalytic 1

degradation of paraquat over TiO 2
TiO2 (1 g L−1 ) and different 0.8 1 wt%
levels of W-doped TiO2 1.5 wt%

Degradation (%)
(25 ppm, W-TiO2 amount-1 2 wt%
g L−1 , pH 6.5) 0.6 2.5 wt%
3 wt%
0.4

0.2

0
0 50 100 150 200
Time (min)

ing weight percent of dopant in TiO2 is depicted in Fig. 8. Results clearly display
enhanced photocatalytic activity of W-doped TiO2 in comparison to bare TiO2 . P25
TiO2 shows 83% degradation, while 94% degradation was observed with 2.5 wt%
tungsten-doped TiO2 under solar illumination. Around 90% degradation occurs in
the first 90 min of irradiation after which the rate of degradation is very low. Doping
improves the photocatalytic efficiency by reducing the bandgap of TiO2 (Bokare et al.
2013). The doped atoms either enter the lattice of TiO2 or disperse on its surface,
thereby affecting the electronic structure and narrow the bandgap of doped TiO2
which absorbs under visible light illumination. The results imply that W-doped P25
(TiO2 ) can significantly improve the photocatalytic degradation as compared to bare
P25 (TiO2 ) due to induced bandgap contraction leading to the enhancement of optical
absorption of photocatalyst under visible illumination. Also, doping decreases the
crystallite size which represents the specific surface area of the catalyst which in turn
affects the photoactivity. The smaller the size and the greater the surface area, the
more the light received per unit area and the higher the electronic excitations which
results in an increase in the photo-efficiency of the catalyst. Hence, a low percentage
degradation was observed for 3 wt% W-doped TiO2 which has a higher crystallite
size than 2.5 wt% W-doped TiO2 .

4 Conclusions

In summary, the present investigation demonstrates that W-TiO2 (tungsten-doped

P25 TiO2 ) can effectively degrade paraquat herbicide under sunlight irradiation. The
synthesized catalyst has been characterized in detail. Doping with tungsten narrowed
the bandgap energy of the synthesized catalyst to 2.8 eV that relates to the enhance-
ment of photocatalytic activity under visible light. The photocatalytic degradation of
paraquat solution by W-doped TiO2 photocatalysts was experimentally investigated
via its absorption spectra. The results conclude that 2.5 wt% W-doped P25 (TiO2 )
154 M. Kaur et al.

is an optimum and efficient catalyst for the photocatalytic degradation of herbicide

paraquat under sunlight. The catalyst amount of 1 g L−1 , initial concentration of
25 ppm and natural pH of the solution (pH = 6.5) are found to be optimum for
around 94% degradation of paraquat in 3 h under sunlight.

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