RESEARCH ARTICLE

Copyright © 2011 American Scientific Publishers Advanced Science Letters

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Printed in the United States of America
Vol. 4, 108–114, 2011

Synthesis of Ag Doped Nano TiO2 as Efficient Solar

Photocatalyst for the Degradation of Endosulfan
Jesty Thomas∗ , K. Praveen Kumar, and K. R. Chitra
School of Chemical Sciences, Mahatma Gandhi University, Kottayam, Kerala State 686560, India

Silver nanoparticles doped anatase TiO2 nanocrystals were prepared via low temperature hydrothermal route.
The synthesized nanocrystals are highly efficient solar photocatalysts and showed higher photocatalytic activity
than pure nano TiO2 and commercial photocatalyst Degussa P25, under sunlight. Silver nanoparticles for dop-
ing were prepared by a novel, single step chemical reduction and stabilization employing L-Dopa. DRS study
showed that nanosilver doping on TiO2 induces a shift of absorption edge to the visible range and there is a
narrowing of the band gap. The solar photocatalytic efficiency of the synthesized samples was checked by the
photocatalytic degradation of methylene blue and found that photocatalytic activity of TiO2 under solar irradia-
tion was drastically increased by doping silver nanoparticles. Further, the synthesized solar photocatalysts were
used for the degradation of the organochlorine pesticide, endosulfan and achieved near complete degradation
with the highly active calcined nanosilver doped TiO2 catalyst.
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Keywords: Nano TiO2 , Silver Nanoparticle,
GuestSolar Photocatalysis, Organic Pollutant Degradation,
User
Endosulfan.
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1. INTRODUCTION UV assisted degradation of the herbicide mecoprop, but with a
Pesticides have become ubiquitously distributed organic pollu- reduced photocatalytic efficiency compared to Degussa P-25.8
tants, and their occurrence, persistence and potential adverse Photocatalytic treatment using TiO2 combined with solar light
effects are a daily mass-media topic.1 The presence of these was very efficient in the destruction of pesticide Diuron in the top
4 cm of contaminated soils.9 Microwave-assisted photocatalytic
persistent organic pollutants (POPs) in the environment is of
degradation of atrazine on TiO2 nanotubes has been studied by
grave public concern and research is intensifying in the area
Zhanqi et al. and complete degradation was obtained.10 In the
of remediation of these contaminants. These compounds are not
present study, we have synthesised silver nano particle doped
susceptible to degradation in the environment and are accumu-
TiO2 and was used for the degradation of the highly toxic chlori-
lated or transported to long distances and biomagnified in the
nated hydrocarbon pesticide  endosulfan (C9 H6 Cl6 O3 S), under
food chain. Conventional biological treatment processes for the
sunlight.
removal of POPs are very slow or ineffective. The traditional
Although TiO2 is a good photocatalyst, due to the wide band
physico-chemical treatments such as adsorption on activated car-
gap (3.2 eV) of TiO2 , an ultraviolet irradiation is necessary for
bon, nano-filtration and ozonation are efficient in comparison
photocatalysis.11 This has consequent implications for the use of
with others but have inherent limitations in applicability, effec-
TiO2 as solar light activated catalyst, because the majority of
tiveness and cost.2–4
sunlight consists of visible light and only a 3–5% UV light. More
Both the stereo isomers of the organochlorine pesticide endo- practical applications can be achieved if the photocatalytically
sulfan, viz.,
and  endosulfan are resistant to direct photolysis active region is extended to the visible region (400–800 nm).12
in soil and aquatic systems, but oxidized to endosulfansulfate Hence in the present work we have made an attempt to synthesize
by microorganisms which is resistant to further biodegradation.5 novel TiO2 photocatalysts with reduced band gap and enhanced
Endosulfansulfate is equally toxic and more persistent than the activity under solar light for the degradation of  endosulfan.
parent compound. Recently, photocatalysis involving TiO2 is Silver nanoparticles were synthesized by a novel strategy, i.e.,
attracting interest in the degradation of endocrine disrupting in a single step from silver nitrate (AgNO3 ) by chemical reduc-
chemical compounds and pesticides.6 Titania aqueous disper- tion technique employing a biologically active molecule L-Dopa
sions were found effective for the photocatalytic decomposition (Scheme 1). Usually during the synthesis of silver nanoparticles,
of the herbicide metolachlor with a t1/2 of 21 minutes with it is very difficult to control its particle size. Also after its forma-
UV irradiation7 and nanosized TiO2 colloids were used for the tion from silver ions by reduction, they need to be stabilized for
further use. But here we found that L-Dopa is an excellent reduc-
∗
Author to whom correspondence should be addressed. ing agent and can stabilize the colloidal nanoparticles through an

108 Adv. Sci. Lett. Vol. 4, No. 1, 2011 1936-6612/2011/4/108/007 doi:10.1166/asl.2011.1192

Adv. Sci. Lett. 4, 108–114, 2011 RESEARCH ARTICLE

Methylene blue was obtained from Rankem, Silver nitrate

HO H3N (AgNO3 ), Sodium hydroxide (NaOH) and L-Dopa were pur-
chased from Aldrich chemicals.  endosulfan standard was
COO
obtained from Sigma-Aldrich Chemical Co., GR grade anhydrous
HO
sodium sulphate, dichloromethane and UniSolv grade toluene
were purchased from M/s Merck Chemicals. All these chemicals
were used without further purification. Deionized water was used
through out the experiments.
Scheme 1. Structure of L-Dopa.

2.2. Synthesis of Silver Nanoparticles

electrostatic interaction so that no other stabilizing agents were
used for the stabilization of silver nanoparticles.
The photocatalytic activity of the synthesized samples under
sunlight was studied by the degradation of methylene blue (MB)
and compared with pure anatase nano TiO2 powder and com-
mercial photocatalyst Degussa-P25. Further, the as synthesized
highly efficient photocatlysts were used for the degradation of
highly persistent pesticide  endosulfan. We found that near com-
plete degradation of  endosulfan is possible by solar photocatal-
ysis using the synthesized silver doped TiO2 nanoparticles.
2. EXPERIMENTAL DETAILS
2.1. Materials
Analytical grade titanium (IV) isopropoxide (Ti[OC3 H7 ]4 ) pur-
chased from Acros Organics was used for the synthesis.
Preparation of silver nanoparticles were carried out by mixing
30 mL, 670 M silver nitrate, 25 L, 0.165 M NaOH and
10 L, 0.01 M L-DOPA. The color of the solution slowly turned
to bright yellow due to the formation of silver nanoparticles.
Colour photograph of synthesized silver nanoparticle is given
in Figure 1(a). The formation of nanoparticles was confirmed
through absorption spectral analysis and TEM image.
2.3. Synthesis of Nano Silver Doped TiO2
Silver nanoparticles synthesized by the above method were added
to 7.0 ml of titanium (IV) isopropoxide, with constant stirring
to get pale yellow precipitate. Distilled water was added to this
precipitate until precipitate formation ceased. The total volume
of the precursor is 70 ml and stirring was continued for 1 hr.
The mixture was transferred into a stainless steel teflon lined
autoclave (100 ml) and the hydrothermal reaction proceeded at

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Absorbance

0
0.2

0.1

0.0

200 400 600 800

Wavelength, nm

HO
(c) (d) OH
HO

HO
NH3
OOC
OOC
NH3 OH
NH3 OOC OH
HO Ag
COO
H3N
HO
NH3 COO
H3N
COO

HO OH
50 nm HO
HO

Fig. 1. (a) Colour photograph of synthesized silver nanoparticle. (b) Absorption Spectrum of silver nanoparticles recorded at different time intervals. (c) TEM
image of synthesized silver nanoparticles. (d) Schematic representation of L-Dopa capped silver nanoparticles.

109
RESEARCH ARTICLE Adv. Sci. Lett. 4, 108–114, 2011

180  C for 2.0 hrs. After hydrothermal treatment, the powders 101
were filtered, washed with water and acetone, respectively, and
dried at 80  C. This sample is designated as TLS1. To study
105
the effect of calcination, TLS1 is calcinated at 300  C for 3 hrs 200
004 211 204 TLS2
(TLS2). Pure nano TiO2 powder (PT) also was synthesized using 215
the above procedure without the addition of silver nanoparticles.

Intensity (a.u.)
The X-ray diffraction patterns (XRD) of the synthesized sam-
ples were obtained on a Brucker D8 Advanced Diffractometer
using Cu K
as radiation. The diffused reflection spectra (DRS) TLS1
of the samples were performed using a UV-2450 Shimadzu UV-
visible spectrophotometer. The photoluminescence (PL) spectral
measurements were made with the synthesized TiO2 nanopar-
ticles using Shimadzu RF-5301 spectrofluorophotometer at an
PT
excitation wavelength of 300 nm. The BET specific surface area
of the powders was measured via nitrogen adsorption, using a
surface area analyzer (Micromeritics, Gemini, USA). A Jeol JSM
10 20 30 40 50 60 70 80 90
6500F scanning electron microscope was used for FESEM stud-
2 Theta
ies. TEM images were taken using a Jeol JEM-3010 transmission
electron microscope. Fig. 2. XRD patterns of PT, TLS1 and TLS2.
The photocatalytic activity of the synthesized samples was
assessed by photocatalytic degradation of methylene blue. For a
typical photocatalytic experiment 0.1 g of synthesized nanocrys- new band at 408 nm, which is the characteristic plasmon absorp-
talline TiO2 was suspended in 100 ml of 50 ppm methylene tion for silver nanoparticles. The formation of silver nanoparticles
blue (MB) aqueous solution. The resulting suspension was equi- was confirmed by TEM image (Fig. 1(c)). The results clearly
librated by stirring in the dark for 30 min. To study the pho- show that L-Dopa is an excellent capping and stabilizing agent
tocatalytic degradation under sunlight the MB–TiO2 suspension for silver nanoparticles and the schematic representation is given
was kept under sunlight at ambient temperature for 70 min. from in Figure 1(d).
12.00 noon to 1.10 noon. The samples were withdrawn at differ-
ent time intervals and centrifuged at 6000 r.p.m. to Delivered
remove the by Ingenta to:
TiO2 particles. The absorbance of MB was measured at 660Guest nm User3.1. XRD Analysis
using a UV-3101 PC UV-VIS-NIR Shimadzu scanning spec- IP : 122.172.114.214
X-ray diffractograms (XRD) of silver doped (TLS1 and TLS2)
trophotometer. It was observed that no detectableSun, 12 Dec
degradation of 2010
and 23:56:21
undoped samples (PT) are shown in (Fig. 2). XRD patterns
MB occurs without TiO2 or solar irradiation alone. reveal that the samples show a high degree of crystallinity and the
To study the degradation of pesticide  endosulfan under solar crystalline phase are of typical anatase (JCPDS, No. 21-1272).
irradiation using the synthesized silver doped and undoped TiO2 There is slight increase in crystallinity of the sample on doping
samples, an aqueous solution with a  endosulfan concentration, silver nanoparticles but no phase change is observed. Hence it is
350 ppb (100 ml) was stirred with the samples PT, TLS1 and clear that silver doping alters the crystallinity but not the crystal
TLS2 (0.1 g) in separate experiments. The resulting suspension structure. After calcination at 300  C the crystallinity of the sam-
was equilibrated by stirring in the dark for 30 min. and then kept ple again increased but there is no phase change in the sample
under direct sunlight from 12.00 noon to 1.00 noon. Samples were (TLS2).
withdrawn at regular intervals, centrifuged and extracted three However, there are no obvious peaks showing the presence of
times with dichloromethane. The combined organic layer is then silver in the XRD patterns of TLS1 and TLS2 and is due to the
dried over anhydrous sodium sulphate and concentrated, which low silver content.13 14 The nanocrystallite size of the synthe-
is then reconstituted in toluene prior to gas chromatographic
sized samples was estimated using Scherrer’s equation; DXRD =
analysis.  endosulfan concentrations in the photocatalytic experi-
0.9/ cos , where D is the crystallite size,  is the wavelength
ments were determined by gas chromatograph equipped with elec-
of X-ray used,  and  are full width at half maximum intensity
tron capture detector (GC-ECD) (Shimadzu GC 2010A) with an
(in radian) (FWHM) of XRD diffraction lines and half diffrac-
autosampler and autoinjector. A capillary column, DB-5 (30 M ×
tion angle 2, respectively. The crystallite sizes of samples are
0.25 mm × 0.25 m) (Agilent Technologies, USA) was used for
given in Table I and is clear that doping of silver nanoparticle
the GC-ECD analysis as well as for the partitioning of the par-
did not alter the crystallite size of the samples but the calcination
ent pesticide and other photolysis product in subsequent GC-MS
analysis. Sample taken at 60 min. was extracted and subjected process slightly increased the crystallite sizes.
for intermediate or end product analysis with GC-MS determina-
tion in electrospray ionization, scan mode (EI-SCAN) (Shimadzu
Table I. BET surface area, particle size, crystallite size and band gap
GCMS QP2010). of PT, TLS1 and TLS2.

Surface area Particle size Crystallite size Band

3. RESULTS AND DISCUSSION Sample (m2 /g) (DBET ) (nm) (DXRD ) (nm) gap (eV)
Figure 1(b) shows the absorption spectra of a solution containing PT 119
55 13.0 13.1 3.23
AgNO3 and NaOH after the addition of L-DOPA recorded at dif- TLS1 113
9 13.5 13.7 2.92
TLS2 93
34 16.5 15.8 2.87
ferent time intervals. The figure clearly shows the formation of a

110
Adv. Sci. Lett. 4, 108–114, 2011 RESEARCH ARTICLE

3.2. Raman Spectra 1.6

Figure 3 depicts the Raman spectra of the synthesized samples.
The peaks at 399, 515, and 637 cm−1 in PT, TLS1 and TLS2 cor- 1.4

responds to the allowed Raman active modes of anatase crystals. 1.2

Absorbance (a.u.)
The presence of silver nanoparticles on the TiO2 surface slightly
reduced the intensities of the peaks in TLS1 and TLS2 which is 1.0
in good agreement with the earlier report.15 But the intensities of 0.8
the peaks of TLS2 is higher than that of TLS1 and this may be
due to the increase in crystallinity of TLS2 during calcination as 0.6
TLS2
is evident from XRD. TLS1
0.4 PT

3.3. Surface Area Analysis 0.2

BET surface areas measured for the synthesized samples are 0.0
given in Table I and show that the surface areas of the sam-
ples are high compared to earlier reports.16 17 Doping of silver 300 400 500 600 700
nanoparticles does not induce appreciable change in surface area. Wavelength (nm)
But there is a decrease in surface area after calcination and is due Fig. 4. Diffuse reflectance absorption spectra of PT, TLS1 and TLS2.
to the increase in crystallite size during calcination. The aver-
age nanoparticle sizes were calculated from BET surface area
absorption band around 400 nm may be attributed to the absorp-
using the equation; DBET = 6000/S, where DBET is the average
tion of the silver nanoparticles, adsorbed on the surface of TiO2
nanoparticle size (nm),  is the powder density (g/cm3 ), S is the
particles.20
specific surface area (m2 /g). The results are shown in Table I and
The band gap energies of the synthesized samples were calcu-
are comparable with the average nanocrystallite size determined
lated by the equation;
using Scherrer’s equation.
Eg = 12398/ Ref. [21]

3.4. Diffuse Reflectance Spectra

To investigate optical absorption properties of the synthesized where Eg is the band gap (eV) and  (nm) is the wavelength
samples the diffuse reflectance absorption spectra Delivered
(DRS) of PT,by Ingenta to:
of the absorption edges in the spectrum. The band gap values
TLS1 and TLS2 were examined in the range 300–750 nm and the Guest User
are given in Table I and the values indicate that silver dop-
results are shown in Figure 4. It is clear from the figureIPthat
: 122.172.114.214
TiO2 ing reduced the band gap of TiO2 nanocrystals. The band gap
nanocrystals without silver nanoparticles (PT) has Sun, 12 Dec
absorption narrowing
in 2010 23:56:21was primarily attributed to the substitution of silver
the UV region and is ascribed to charge transfer from valence nanoparticles which introduced electron states into the band gap
band (mainly formed by 2p orbitals of oxide anion) to the con- of TiO2 to form a new lowest unoccupied molecular orbital. The
duction band (mainly formed by 3dt2g orbitals of Ti4+ cation).18 shift of absorption edge of TiO2 to visible range and narrowing
The samples with silver nanoparticles (TLS1 and TLS2) showed of band gap increased the photocatalytic activity of TiO2 in the
significant absorption in the visible region which is in good visible region.
agreement with the earlier reports. 13 19
The red shifted photore- Further, the absorption spectrum of TLS2 reveals more absorp-
sponse of TLS1 and TLS2 as observed in the figure may lead tion in the visible region than TLS1 which indicates the existence
to high photocatalytic activity under visible region which helps of surface states.22 The most possible mechanism to account for
in the enhancement of photocatalytic activity under sunlight. The the observed absorption might involve oxygen vacancies pro-
duced by thermal treatment, which form localization levels within
the band gap.22
35000
3.5. Morphological Analysis
30000 FESEM and TEM images of the silver doped samples are
given in Figure 5. FESEM (Figs. 5(a and b)). In TEM images
PT
25000 (Figs. 5(c and d)) Ag nanoparticles are distinguishable and appear
Intensity (a.u.)

as dark dots on the surface of the TiO2 particles. Also, there is a

20000 TLS2 possibility for silver to be incorporated into the interstitial posi-
TLS1 tions of the TiO2 semiconductor particles. It is also clear that
15000 the crystallinity has been increased which is indicated by the
increased crystal size with well-developed faces. This observa-
10000 tion is supported by the XRD spectrum (Fig. 2).
5000 3.6. Photoluminescence Studies
The photoluminescence emission spectra (PL) of the synthesised
0
200 300 400 500 600 700 800 samples were studied in the range of 200–600 nm to investigate
Raman shift (cm–1)
the separation efficiency of charge carriers and the results are
shown in Figure 6. It is evident from the figure that the PL inten-
Fig. 3. Raman spectra of PT, TLS1 and TLS2. sity of TiO2 was decreased with silver doping. The lower PL

111
RESEARCH ARTICLE Adv. Sci. Lett. 4, 108–114, 2011

(a) (b)

(c) (b)

Fig. 5. FESEM of TLS1 (a) TLS2 (b) and TEM images of TLS1 (c) and TLS2 (d).
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intensity shows that the rate of recombination between electron enhance the efficiency of photocatalysis.23 24 For samples TLS1
23 IP : 122.172.114.214
and holes is low. The electrons are excited from valance band and TLS2, silver nanoparticles plays an important role in the
(VB) to conduction band (CB) of TiO2 under UVSun, 12 Dec
irradiation and 2010 23:56:21
interfacial charge transfer and in the decrease in rate of electron-
generate photoexcited electrons and holes. Although doping with hole recombination. Silver nanoparticles could act as an effec-
silver narrows the band gap of TiO2 samples, the recombination tive electron scavenger to trap the photo induced electrons and
of electrons and holes are relatively slow which is evident from holes of TiO2 leading to the reduction of electron–hole recom-
PL spectra. bination and thus improving the photocatalytic efficiency. The
As is well known, TiO2 exhibit poor photocatalytic efficiency electrons trapped in silver sites were subsequently transferred to
since the majority of photogenerated charge carriers undergo the surrounding adsorbed O2 . It can be supported by PL emission
recombination. In the present system, silver nanoparticles act as spectra, which have been widely used to investigate the fate of
electron acceptors and sinks for the charge carriers which will electron hole pairs in semiconductor particles since PL emission
results from the recombination of free carriers.20 25
3.0
3.7. Photocatalytic Activity
2.5 To investigate the photocatalytic activity of synthesized TiO2
PT
2.0 samples in solar light, the degradation of MB was studied
in presence of PT, TLS1 and TLS2 nanoparticles under sun-
1.5 TLS1
light. For comparison, photocatalytic studies were also performed
Intensity (a.u.)

1.0 TLS2 with commercially available photocatalyst, Degussa P25 and the
0.5
results are depicted in Figure 7. The activity of different samples
in sunlight is in the order TLS2 > TLS1 > PT > Degussa P25.
0.0 Silver doped TiO2 samples show higher activity than undoped
–0.5 TiO2 and Degussa P25. Diffuse reflectance spectra of silver
doped TiO2 samples showed significant absorption in the visi-
–1.0
ble region which enhance the photocatalytic activity in the vis-
–1.5 ible region. The high activity of silver doped TiO2 samples is
–2.0
mainly attributed to the decrease in band gap (3.23 to 2.87 eV)
200 300 400 500 600 700 so that visible light is enough to excite electron from valence
Wavelength (cm–1)
band to conduction band. Silver nanoparticles could act as an
effective electron scavenger to trap the conduction band elec-
Fig. 6. Photoluminescence emission spectra (PL) of PT, TLS1 and TLS2. trons of TiO2 .23 In silver doped TiO2 the silver nanoparticles

112
Adv. Sci. Lett. 4, 108–114, 2011
100
TLS2
TLS1
90 PT
80
% Degradation of MB
70
Degussa P 25
60
50
40
30
20
10
10 20 30 40 50 60 70
Time in min
Fig. 7. Photocatalytic activity of PT, TLS1, TLS2 and Degussa P25 under
sunlight.
play an important role in the interfacial charge transfer and in
the elimination of electron-hole recombination as is evident from
PL spectra, which would be beneficial for the high photocatalytic
activity. The activity of PT is less because here electrons can-
not be excited from valence band to conduction band by visible
light irradiation due to the large band gap as calculated from
DRS (3.23 eV). In this case an ultraviolet irradiation Delivered
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for the excitation of electrons from valence band to conduction Guest User
band to carry out photocatalysis, which accounts forIP : 122.172.114.214
only small
fraction of the solar light. Also the efficiency ofSun, 12 Dec 2010
the photocatal-
ysis depends on the effectiveness of the photocatalytic process
in transferring the photoinduced e− /h+ pair from the particle
volume to the particle surface and subsequently to the surface-
adsorbed species. In PT there is no intermediate level to trap the
electron and the recombination possibility of electrons and holes
is enhanced and the free electron or holes available for the pho-
tocatalysis is less, subsequently the efficiency of photocatalysis
also is less.
It is well known that it is the anatase polymorph rather than the
brookite or rutile polymorph that has the highest photocatalytic
activity. The most active commercially available photocatalyst
(Degussa P25) has an anatase content of 75% and 25% of rutile
content.26 From the XRD pattern it is evident that the synthesized
samples (PT, TLS1 and TLS2) are purely anatase and hence it
shows higher activity than Degussa P25.
The synthesized silver doped samples (TLS1 and TLS2) are
highly efficient photocatalysts as is evident from the MB degra-
dation studies. The sample TLS2 shows higher photocatalytic
activity than the sample TLS1 (Fig. 7) and is due to the increase
in crystallinity of TLS2, which is clear from the XRD data. How-
ever, no direct relation was found between the BET areas and the
catalytic activity of the catalysts as in earlier report.27 The previ-
ous reports show that calcination of samples and UV irradiation
was required for effective photocatalysis, also the UV irradiation
time for the degradation of MB is high (60 to 120 min).28 29
The studies which deals visible light photocatalysis of MB using
doped TiO2 also required high temperature calcination (600  C)
and longer irradiation time (60–120 min).30 31
RESEARCH ARTICLE
But we have used low temperature hydrothermal route to pre-
pare efficient photocatalyst which is active under solar light with
out any high temperature treatment. Also silver doping could
replace artificial UV light irradiation by sunlight. Hence it is clear
that silver doping in TiO2 can give highly efficient photocatalysts
which are active under sunlight.
In addition to higher photocatalytic activity, the hydrother-
mally synthesized TiO2 samples are easier to separate from the
aqueous media than Degussa P25. Degussa P25 forms a milky
white turbid suspension in aqueous media. Though the synthe-
sized samples have equal or less particle size they do not form
turbid suspension. Also the synthesized catalysts settle faster and
it is easier to separate from the reaction mixture by centrifuga-
tion. This enabled recyclability of the synthesized nanophotocat-
alysts after centrifugation at the end of each photocatalytic cycle
and the recycled catalyst was found efficient and stable for more
than six cycles.
Degradation of the nonbiodegradable pesticide  endosulfan,
was also investigated in the light of the interesting photocat-
alytic activity of the synthesized nanoparticles with MB. The
photocatalytic activity of PT, TLS1 and TLS2 nanoparticles with
the organochlorine pesticide under sunlight was studied in sep-
arate experiments. Figure 8 shows the degradation kinetics of 
endosulfan with the nanoparticles at an initial concentration of
350 ppb, which is close to the maximum aqueous solubility of
 endosulfan. Concentration of the organochlorine pesticide 
endosulfan was determined by GC-ECD analysis. As expected,
here also the more crystalline nanoparticle sample TLS2 exhib-
to:photocatalytic activity followed by TLS1 and PT. In
ited highest
TLS2-Endosulfan system, substantial reduction in the concentra-
tion of  endosulfan was observed in the initial 20 minutes at a
t1/2 23:56:21
of 13 minutes. It was observed that more than 98% of the
pesticide was decomposed in 60 minutes. The GC-MS analysis
in EI-SCAN mode of the sample taken at 60 minutes confirmed
the almost complete mineralization of  endosulfan. The envi-
ronmental degradation products of endosulfan as proposed by
Bakouri et al.,32 such as the immediate hydrolysis product endo-
sulfan diol, the oxidation product endosulfan sulfate or the further
decomposition products endosulfan ether, endosulfan hydroxyl
ether or endosulfan lactone were not detected in the system. To
ensure degradation rather than adsorption, the experiment was
1.0
0.8
0.6
Ct/C0
PT
0.4
0.2
TLS1
TLS2
0.0
0 10 20 30 40 50 60
Time, min.
Fig. 8. Photocatalytic degradation of  endosulfan using PT, TLS1 and
TLS2 under sunlight.
113
RESEARCH ARTICLE
repeated with the same TLS2 nanoparticles (after regenerating it
from the photocatalytic system by centrifugation), with the same
initial concentration of endosulfan for six more cycles. Samples
were analyzed for endosulfan concentration at the end of 60 min-
utes. The TLS2 photocatalytic system was found stable and effi-
cient after the repeated experiments with consistent endosulfan
degradation capability. In aqueous systems, though endosulfan
resist direct photolysis, it is clearly observed that it undergoes
near complete photodegradation with silver doped nano TiO2
particles. The heterogeneous photocatalysis with TiO2 nanopar-
ticles accelerated the decomposition of otherwise recalcitrant 
endosulfan and silver doping shifted the photocatalysis to visible
region to attain efficient degradation under sunlight. The results
suggest the potential of silver doped TiO2 nanomaterials in envi-
ronmental pollutant remediation applications.
4. CONCLUSIONS
Anatase nanocrystals with enhanced photocatalytic activity under
solar irradiation have been successfully synthesized by low
temperature hydrothermal route by silver doping. Silver nanopar-
ticles for doping were prepared by simultaneous chemical reduc-
tion and stabilization employing L-Dopa, without any additional
stabilizing agent. The hydrothermally synthesized TiO2 samples
showed higher photocatalytic activity under sunlight than the
commercially available photocatalyst Degussa P25 and could
completely degrade the organochlorine pesticide, endosulfan by
sunlight irradiation. Also the synthesized catalysts settle faster
and it is easier to separate from the reaction mixture which pro- by Ingenta to:
Delivered
motes the reusability of these photocatalysts. Decrease in band
gap in silver doped samples by the formation of an intermedi-
Guest User
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ate level is the major reason for the high photocatalytic activ-
ity of these samples under sunlight. The presentSun,
study 12 Dec 2010 23:56:21
suggests
that silver doped TiO2 can be used for the development of an
environmentally sustainable photocatalytic treatment process for
the degradation of persistent organic pollutants using sunlight in
place of an artificial light.
Acknowledgments: The authors wish to thank the Depart-
ment of Science and Technology (DST), India, for financial sup-
port under woman scientist scheme (WOS-A).
References and Notes
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Eng. 17, 673 (1995).
114
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3. E. Wittmann, P. Cote, C. Medici, J. Leech, and A. G. Turner, Desalination
119, 347 (1998).
4. P. Roche and M. Prados, Ozone-Sci. Eng. 17, 657 (1995).
5. H. M. Shivaramaiah and I. R. Kennedy, J. Environ. Sci. Health Part B 41, 895
(2006).
6. D. Dong, P. Li, X. Li , Q. Zhao, Y. Zhang, C. Jia, and P. Li, J. Hazardous
Materials 174, 859 (2010).
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Received: 30 May 2010. Accepted: 6 July 2010.