Journal of Materials Science: Materials in Electronics (2018) 29:3657–3664

https://doi.org/10.1007/s10854-017-8296-1

Improved photodegradation activity of ­SnO2 nanopowder

against methyl orange dye through Ag doping
N. Manjula1,2 · G. Selvan2 · A. R. Balu3

Received: 26 October 2017 / Accepted: 17 November 2017 / Published online: 21 November 2017
© Springer Science+Business Media, LLC, part of Springer Nature 2017

Abstract
Silver doped tin oxide ­(SnO2:Ag) nanopowders were synthesized by a simple soft chemical route with 0, 5, 10 and 15 wt%
concentrations of Ag. The structural, morphological, optical, photoluminescence and photocatalytic properties of the syn-
thesized samples were studied and the results obtained are reported in this paper. XRD studies confirm the polycrystalline
nature of the synthesized samples. The undoped and doped samples exhibit a strong (1 0 1) preferential growth. Decreased
crystallite size is observed with Ag doping. Nanosized grains were observed for the doped samples. Peak related to Sn–O–Sn
lattice vibration is observed for both the undoped and doped samples in the FTIR spectra. Peaks related to oxygen vacancies
were observed at 362 and 499 nm for all the samples in the PL spectra. Enhanced photocatalytic activity was observed for
the doped samples and the ­SnO2:Ag nanopowder with 10 wt% Ag doping concentration exhibited maximum photodegrada-
tion efficiency against the degradation of methyl orange dye.

1 Introduction pairs in semiconductor particles under illumination by vis-

In recent years, metal oxide semiconductor photocatalysts
have attracted considerable attention due to their potential
applications in hazardous waste remediation and energy
problems with abundant solar light [1]. Among the metal
oxide semiconductor photocatalysts, tin oxide (­ SnO2) is a
wide band gap n-type semiconductor which has high opti-
cal transparency, electrical conductivity, high photosensi-
tivity and chemical sensitivity [2]. Due to its good optical
properties, chemical and mechanical stability, ­SnO2 is used
in many applications such as oxidation catalysis, gas sen-
sors, solar cells, transparent conducting electrodes, lithium
ion batteries, etc [3]. In the field of photocatalysis, ­SnO2
seems to be an interesting material due to its different mor-
phologies, high photochemical stability, strong oxidizing
power and non-toxic nature [4]. The photocatalytic activ-
ity mainly relies on the generation of electron–hole (­ e−/h+)
* G. Selvan
gselvan96@gmail.com
1
PG and Research Department of Physics, Bharathiyar
University, Coimbatore, Tamilnadu, India
2
PG and Research Department of Physics, Thanthai Hans
Roever College, Perambalur, Tamilnadu, India
3
PG and Research Department of Physics, AVVM Sri
Pushpam College, Poondi, Tamilnadu, India
ible/UV light. However, a quick recombination of the pho-
togenerated electron and hole prevents augmentation of the
photocatalytic efficiency. To counter this challenge many
strategies such as semiconductors combination, transition
metal doping and metal deposition has been adopted [5].
Eventhough, ­SnO2 seems to be a promising semiconduc-
tor material for photovoltaic applications, its photocatalytic
efficiency is often restricted because of poor quantum yield
caused by the fast recombination rate and ineffective utiliza-
tion of photo-generated electron–hole pairs [6]. To improve
the photocatalytic efficiency of S­ nO2, doping has been per-
formed as the dopant ions could introduce lattice defects
which could lower its effective optical band gap, thus leading
to a better photoactivity [7]. Silver is noble metal of group
I which possess high electrical conductivity which facili-
tates fast electron transfer and low work function favoring
the formation of good band alignment and Ag doped/loaded
photocatalyst showed enhanced photocatalytic activity due
to the surface plasmon resonance phenomenon under light
irradiation [8]. Improved photocatalytic activity has been
reported earlier for Ag-doped CdS thin films [9] and Ag-
doped ­TiO2 nanoparticles [10]. Motivated by these results,
in the present work Ag-doped ­SnO2 ­(SnO2:Ag) nanopow-
ders were synthesized by a cost effective chemical method
with different concentrations of Ag (0, 5, 10 and 15 wt%).
Among the various chemical methods used to synthesize

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undoped and doped nanoparticles the cost effective simple

chemical method adopted here has several advantages such
as low cost, rapid synthesis, ease to dope, low preparation
temperature, etc [11]. The synthesized ­SnO2:Ag nanopow-
ders was characterized by techniques like XRD, SEM, TEM,
UV–Vis–NIR, FTIR and PL. The photocatalytic activity was
tested against the photodegradation of methyl orange dye
under visible light irradiation and the results obtained are
reported.

2 Experimental details

Ag-doped ­SnO2 ­(SnO2:Ag) nanopowders were prepared by

a simple soft chemical route with 0, 5, 10 and 15 wt% Ag
doping concentrations. Undoped S ­ nO2 nanopowder was pre-
pared using tin(II) chloride [­ SnCl2·2H2O] as the precursor
salt. Tin(II) chloride with 0.1 M was dissolved in a mixture
of HCl and de-ionized water in the volume ratio of 1:13 in
a total volume of 140 ml. The pH value of this solution was
raised to 10 by adding 10 ml liquid ammonia. The resultant
solution was stirred well for 2 h and kept undisturbed for
4 h. The settled precipitates were cleaned two times with
de-ionized water and then calcined at 200 °C for 1 h in a
muffle furnace. The residual product was then crushed using
an agate mortar to get grey colored S ­ nO2 nanopowders. To
achieve Ag doping, silver nitrate [Ag(NO3)2] with concentra-
tions 5, 10 and 15 wt% was added to the precursor solution
and the same procedure used to synthesize pure S ­ nO2 nano-
powders was adopted to get ­SnO2:Ag nanopowders. X-ray
diffractometer (PANanalytical-PW 340/60 X’pert PRO) with
CuKα radiation (λ = 1.5406 Å) is used to analyse the crys-
tal structure of the samples. Scanning electron microscope
(HITACHI S-3000 H) and transmission electron microscope
(200 kV Tecnai-20 G2) are used to examine the surface mor-
phology of the samples. The functional groups present in
the samples were identified using Perkin Elmer RX-1 FTIR
spectrophotometer. Optical studies were performed using
Perkin Elmer UV–Vis–NIR double beam spectrophotometer
(LAMBDA 35). Photocatalytic activity of the samples was
evaluated by the photodegradation of methyl orange (MO)
dye under visible light, irradiated from a 100 W incandes-
cent lamp.
3 Results and discussion
Figure 1 shows the XRD patterns of the S ­ nO2:Ag nanopo-
wders. Polycrystalline nature is observed for all the sam-
ples and the diffraction peaks fit well with tetragonal ­SnO2
(JCPDS Card No. 88-0287). All the samples exhibit a strong
(1 0 1) preferential growth. No peaks related to metallic Ag
or ­Ag2O were detected within the instrumental sensitivity,
Fig. 1  XRD patterns of ­SnO2:Ag nanopowders
indicating that silver ions were well incorporated into the
­SnO2 lattice. This is in contrast with the results reported by
Mouchaal et al. [12] where they detected A ­ g2O in the XRD
pattern of 4 wt% Ag, in codoped S ­ nO2 thin films, which
confirms that the chemical route adopted here is very effec-
tive in synthesizing homogenous S ­ nO2:Ag nanopowders. It
was also found that the major (1 0 1) peak of pure ­SnO2
shifted towards lower 2θ angle with Ag doping which might
be due to the expansion of PbS lattice due to the substitution
of smaller sized S­ n2+ ions (0.93 Å) with larger sized A ­ g+
ions (1.22 Å). Similar result has been reported earlier by
Narasimman et al. [13] for Ag-doped CdS thin films. The
lattice constants (a and c) of pure S
­ nO2 (Table 1) increases
with increase in Ag doping concentration. The calculated
lattice parameter values of the ­SnO2:Ag nanopowders are
found to be higher than the bulk (a = 4.737 Å, c = 3.186 Å)
suggesting that the samples are under strain with Ag doping.
The crystallite size (D) and strain (ε) values of the
­SnO2:Ag nanopowders are calculated using the formulae
[14]:
0.9 𝜆
D= (1)
𝛽 cos 𝜃
𝛽 cos 𝜃
𝜀= (2)
4
where β is the full width at half maximum value of the (1
0 1) peak in radians, λ is the wavelength of the X-ray used

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Table 1  Crystallite size, Ag doping con- Crystallite Strain ‘ε’ × 10−3 Lattice constant Photodegradation efficiency (%)
strain, lattice parameter and centration (wt%) size ‘D’ (nm)
photodegradation efficiency a (Å) c (Å) 60 min 120 min 180 min
values of the ­SnO2:Ag
nanopowders 0 27.62 0.758 4.768 3.210 41.67 56.67 75.04
5 25.14 0.864 4.842 3.287 53.85 71.53 88.22
10 23.04 0.957 4.912 3.363 68.85 84.43 93.44
15 23.91 0.904 4.978 3.411 62.50 81.25 90.18

(1.5406 Å) and θ is the Bragg angle. The calculated D and
𝜖 values compiled in Table 1, show opposite trend behav-
ior. Reduction in crystallite size may be due to the reduc-
tion in diffusion rate which makes the nanopowders intact
and due to increased strain in S ­ nO2 lattice with Ag doping.
Decreased crystallite sizes result in a drastical decrement
of photoinduced charges’ recombination, which efficiently
promote photocatalytic reactions [15].
Figres 2 and 3 shows the SEM and TEM images of (a) 0, (b)
5, (c) 10 and (d) 15 wt% Ag-doped S ­ nO2 nanopowders. All the
surfaces appear to be composed of grains with different sizes
and shapes. Nanosized grains are also visible. All the samples
possessed quite large surface area, which was believed to be
an important factor in photocatalytic reactions, in accordance
with small crystallite sizes as evinced from XRD studies.
Figure 4 shows the FTIR spectra of (a) undoped and (b) Ag-
doped ­SnO2 nanopowders. The peaks observed in the range
3150–1500 cm−1 for both the undoped and doped samples are
attributed to O–H stretching vibrations [16]. The peak cor-
responding to –CH3 bending mode is observed at 1402 cm−1
for both the undoped and doped samples [17]. This might be
due to the addition of liquid ammonia to the precursor solu-
tion while synthesizing the samples. The peaks at 1136 and
1023 cm−1 observed for the undoped sample is attributed to
Sn–O–Sn lattice vibrations [18]. The peak at 1136 cm−1 got
shifted to 1121 cm−1 with ­Ag+ doping. The peak at 780 cm−1
observed for the undoped sample corresponds to N–O stretch-
ing vibration [19]. The peaks observed in the wavenumber
range 520–620 cm−1 are related to metal oxygen (MO) bond
which corresponds to the stretching vibrations of Sn–O [20].
Figure 5a shows the absorbance spectra of the S ­ nO2:Ag
nanopowders with 0, 5, 10 and 15 wt% Ag concentrations.
It can be seen that the absorption edge of pure S ­ nO2 shifts
towards lower wavelengths with Ag doping. The optical band
gap ­(Eg) of the S
­ nO2:Ag nanopowders was evaluated from the
reflection spectra using the Kubelka–Munk function F(R) [21]:
(1 − R)2
F(R) =
2R
where R represents the percentage reflectance. The direct
band gap values was calculated by extrapolating the linear
part of the plots of [F(R) × hυ]2 versus hυ (Fig. 5b) at α = 0.
The band gap values of the S ­ nO2:Ag nanopowders with 0, 5,
10 and 15 wt% Ag concentrations were found to be equal to
3.27, 3.35, 3.45 and 3.4 eV, respectively. Increased band gap
values were observed for the doped samples which might
be due to size induced quantum confinement present in the
Ag-doped SnO2 nanopowders [22]. Similar enhancement
in Eg value has been reported earlier for Mn-doped ­SnO2
nanoparticles [23]. Increased band gap values are impor-
tant in preventing the electron–hole recombination which
can enhance the photocatalytic activity of Ag-doped ­SnO2
nanopowders [24].
The room temperature PL spectra of the S ­ nO2:Ag nano-
powders are shown in Fig. 6. The peaks at 499 and 362 nm
are mainly due to oxygen vacancies which form donor
levels in S­ nO2 [25]. The blue emission peaks at 470 and
459 nm are due to the electronic transitions from the tin
interstitials and/or oxygen vacancies [26]. The peak arising
from the recombination of the electrons from the conduc-
tion band and holes in the valence band is observed at
441 nm [27]. The near band edge (NBE) peak due to free
exciton recombination is observed at 408 nm [28]. The
peak attributed to higher level excitonic emission related
to quantum confinement is observed at 324 nm [29].
The photocatalytic activity of the S ­ nO2:Ag photocata-
lysts was examined by studying the oxidative degradation
of methyl orange dye under visible light irradiation. The
photocatalytic experiment was carried out by preparing
reaction suspensions with 6 mg of the photocatalysts into
100 ml of 0.25 M MO solution. The dye solution with
the photocatalysts was stirred in dark for 1 h to maintain
absorption/desorption equilibrium and then illuminated
under visible light at different time intervals (0, 60, 120
and 180 min). After every 1 h interval, 6 ml solution was
withdrawn from the suspension and the catalysts were
separated from it using a centrifuge. The concentration of
MO was analyzed by using Perkin Elmer UV–Visible–NIR
double beam spectrophotometer at λ = 470 nm. The photo-
degradation efficiency of the ­SnO2:Ag photocatalysts was
calculated using the relation [30]:
(3)
( )
C
𝜂 = 1− × 100 (4)
C0
where C is the concentration of MO after irradiation and C0
is the concentration before light irradiation. The calculated

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Fig. 2  SEM images of a 0, b 5, c 10 and d 15 wt% Ag-doped S

­ nO2 nanopowders

efficiency values are compiled in Table 1. It is observed that
the photodegradation efficiency of pure ­SnO2 got enhanced
with Ag doping and among the doped samples the 10 wt%
Ag-doped ­SnO2 photocatalyst exhibited a maximum effi-
ciency of 93.44%. The increased activity observed for the
doped samples might be due to the effective charge trans-
fer ability of ­Ag+ ions. This is in accordance to the results
reported by Vignesh et al. [31]. Figure 7a shows the absorp-
tion spectrum of 10 wt% Ag-doped ­SnO2 photocatalyst as a
function of irradiation time. The absorption peak decreases

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Fig. 3  TEM images of a 0, b 5, c 10 and d 15 wt% Ag-doped ­SnO2 nanopowders

confirming the fact that MO molecules degrades with irra- Under visible light irradiation, electron–hole ­(e−/h+) pairs
diation time and almost 93.44% of the MO molecules gets are produced from the ­SnO2 photocatalyst by the equation:
degraded after 180 min. The mechanism involved in the pho-
SnO2 + h𝛾 → e− + h+
tocatalytic activity of the S
­ nO2:Ag photocatalyts (Fig. 7b)
is as follows:

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Fig. 4  FTIR spectra of S
­ nO2:Ag nanopowders

Fig. 5  a Absorbance spectra of ­SnO2:Ag nanopowders, b plots of [F(R) × hυ]2 versus hυ of ­SnO2:Ag nanopowders

The holes generated reacts with hydroxyl groups and

adsorbed ­H 2O to form hydroxyl radicals (­OH ·) by the
equations:

OH− + h+ → OH⋅

H2 O + h+ → OH⋅ + H+
The ­Ag+ ions act as electron traps generating superoxide
ions ­(O2·−) reaction with ­O2 by the equation:
Ag + e− → Ag−

Ag− + O2 → O⋅−
2
+ Ag
­ H· by
The final product of the reduction may also be O
Fig. 6  PL spectra of S
­ nO2:Ag nanopowders the equation:

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­ nO2 photocatalyst, b photocatalytic activity of ­SnO2:Ag nanopowders
Fig. 7  a Absorbance spectrum of 10 wt% Ag-doped S
2O⋅−
2
+ 2H+ → 2OH⋅
The hydroxyl radicals and superoxide ions are the reac-
tive oxygen species which degrade MO by the equation:
OH⋅ + O⋅− + MO → CO2 + H2 O (degradation of MO molecules)
2 3. S. Ferrari, L.G. Pampilo, F.D. Saccone, Mater. Chem. Phys.
The decreased photocatalytic activity observed for
the 15 wt% Ag-doped S ­ nO2 photocatalyst might be due
to increased crystallite size, loss of stoichiometry which
leads to quantum tunnelling.
4 Conclusion
SnO2:Ag nanopowders were successfully synthesized by
a cost effective simple chemical route with 0, 5, 10 and
15 wt% Ag doping concentrations. Structural studies con-
firmed the polycrystalline nature of the samples. Undoped
and Ag-doped ­S nO 2 nanopowders exhibited tetragonal
crystal structure with a strong (1 0 1) preferential growth.
Nanosized grains are evinced from the TEM images of the
synthesized samples. Photocatalytic activity of pure S ­ nO2
against the degradation of methyl orange got enhanced
with Ag doping. The enhanced photocatalytic activities
observed make ­SnO2:Ag nanopowders suitable for waste
water treatment and other bioremediation processes.
Acknowledgements  The authors thank the Director, STIC Cochin for
the TEM analysis.
References
1. K. Yin, M. Shao, Z. Zhang, Z. Lin, Mater. Res. Bull. 47, 3704
(2012)
2. H. Yuan, J.Q. Xu, Int. J. Appl. Chem. 1, 241 (2010)
177, 206 (2016)
4. P. Kamaraj, R. Vennila, M. Arthanareeswari, S. Devikala, World
J. Pharm. Sci. 3, 382 (2014)
5. Z. Nasir, M. Shakir, R. Wahab, M. Shoeb, P. Alam, R.H. Khan,
M. Mobin, Int. J. Biol. Macromol. 94, 554 (2017)
6. L.R. Zheng, Y.H. Zheng, C.Q. Chen, Y.Y. Zhan, X.Y. Lin, Q.
Zheng, K.M. Wei, J.F. Zhu, Inorg. Chem. 48, 1819 (2009)
7. M.A.M. Al-Hamdi, M. Sillanpaa, J. Duha, J. Mater. Sci. 49,
5151 (2014)
8. D.D. Lin, H. Wu, R. Zhang, W. Pan, Chem. Mater. 21, 3479
(2009)
9. M. Ristova, M. Ristov, P. Tosev, Thin Solid Films 315, 301
(1998)
10. L. Zhang, J.C. Yu, H.Y. Yip, Q. Li, K.W. Kwong, A.W. Xu, P.K.
Wong, Langmuir 19, 10372 (2003)
11. M. Suganya, D. Prabha, S. Balamurugan, A.R. Balu, J. Mater. Sci.
Mater. Electron. 28, 5344 (2016)
12. Y. Mouchaal, A. Enesca, C. Mihoreanu, A. Khelil, A. Duta, Mater.
Sci. Eng. B 199, 22 (2015)
13. V. Narasimman, V.S. Nagarethinam, K. Usharani, Mater. Res.
Innov. (2016). https://doi.org/10.1080/14328917.2016.1264857
14. S. Ravishankar, A.R. Balu, Surf. Eng. 33, 506 (2017)
15. K. Zhang, D. Jing, Q. Chen, L. Guo, Int. J. Hydrogen Energy, 35,
2048 (2010)
16. M.A. Abbasi, D. Ghanbari, M.S. Niasari, M. Hamadanian, J.
Mater. Sci. 27, 4800 (2016)
17. S. Balamurugan, A.R. Balu, K. Usharani, M. Suganya, S. Anitha,
D. Prabha, S. Ilangovan, Pac. Sci. Rev. A 18, 228 (2016)
18. M.A.A. Dakhel, Powder Technol. 237, 333 (2013)
13

3664
19. K.K. Onchoke, C.M. Hadad, P.K. Dutta, J. Phys. Chem. A 110,
76 (2006)
20. N. Manjula, G. Selvan, J. Mater. Sci. (2017). https://doi.
org/10.1007/s10854-017-7380-x
21. P. Pascariu, A. Airinei, M. Grigoras, N. Fifere, L. Sacarescu, N.
Lupu, L. Stoleriu, J. Alloys Compd. 668, 65 (2016)
22. T. Sivaraman, V.S. Nagarethinam, A.R. Balu, Surf. Eng. 32, 596
(2016)
23. K. Anandan, V. Rajendran, Superlattices Microstruct. 85, 185
(2015)
24. L. Kumaresan, M. Mahalakshmi, M. Palanichamy, V. Murugesan,
Ind. Eng. Chem. Res. 49, 1480 (2010)
25. J. Jeong, S.P. Choi, C.I. Chang, D.C. Shin, J.S. Park, B.T. Lee,
Y.J. Park, H.J. Song, Sol. State. Commun. 127, 595 (2003)
13
Journal of Materials Science: Materials in Electronics (2018) 29:3657–3664
26. K. Usharani, A.R. Balu, V.S. Nagarethinam, Surf. Eng. 32, 829
(2016)
27. S.J. Gnanamuthu, S.J. Jeyakumar, I.K. Punithavathi, K. Paras-
uram, V.S. Nagarethinam, A.R. Balu, Trans. Indian Inst. Met. 70,
1503 (2017)
28. Y. Jin, Q. Cui, K. Wang, J. Hao, Q. Wang, J. Zhang, J. Appl. Phys.
109, 053521 (2011)
29. J. Srivind, V.S. Nagarethinam, A.R. Balu, Mater. Sci. Pol. 34, 393
(2016)
30. M. Suganya, A.R. Balu, D. Prabha, S. Anitha, S. Balamurugan, J.
Mater. Sci. (2017). https://doi.org/10.1007/s10854-017-8007-y
31. K. Vignesh, R. Hariharan, M. Rajarajan, A. Suganthi, Sol. State
Sci. 21, 91 (2013)