metals

Article
TiO2–SnO2 Nanocomposites for Photocatalytic Environmental
Remediation under UV-Light
Sandip M. Deshmukh 1 , Santosh S. Patil 2 , Santosh B. Babar 1 , Sultan Alshehri 3 , Mohammed M. Ghoneim 4 ,
Asiya M. Tamboli 5 , Nguyen Hoang Lam 6 , Nguyen Tam Nguyen Truong 6, *, Chang Duk Kim 7 ,
Mohaseen S. Tamboli 5, * , Sanjay M. Khetre 8, * and Sambhaji R. Bamane 9

1 Department of Chemistry, Vishwasrao Naik Mahavidyalay, Shirala 415408, Maharashtra, India;

[email protected] (S.M.D.); [email protected] (S.B.B.)
2 Department of Chemistry and Chemical Engineering, Inha University, 100 Inha-ro, Michuhol-gu,
Incheon 22212, Korea; [email protected]
3 Department of Pharmaceutical Sciences, College of Pharmacy, Almaarefa University, Ad Diriyah,
Riyadh 13713, Saudi Arabia; [email protected]
4 Department of Pharmacy Practice, College of Pharmacy, Almaarefa University, Ad Diriyah,
Riyadh 13713, Saudi Arabia; [email protected]
5 Korea Institute of Energy Technology (KENTECH), 200 Hyeokshin-ro, Naju 58330, Jeollanam-do, Korea;
[email protected]
6 School of Chemical Engineering, Yeungnam University, 280 Daehak-ro, Gyeongsan 38541, Korea;
[email protected]
7 Department of Physics, Kyungpook National University, 80 Daehak-ro, Buk-gu, Daegu 41566, Korea;
[email protected]
8 Nanomaterials Research Laboratory, Department of Chemistry, Dahiwadi College,





 Dahiwadi 415508, Maharashtra, India
9 Department of Chemistry, Sushila Shankarrao Gadhave Mahavidyalaya,
Citation: Deshmukh, S.M.; Patil, S.S.;
Babar, S.B.; Alshehri, S.; Ghoneim, Khandala 412802, Maharashtra, India; [email protected]
M.M.; Tamboli, A.M.; Lam, N.H.;
* Correspondence: [email protected] (N.T.N.T.); [email protected] (M.S.T.);
[email protected] (S.M.K.)
Truong, N.T.N.; Kim, C.D.; Tamboli,
M.S.; et al. TiO2 –SnO2
Nanocomposites for Photocatalytic
Abstract: The photocatalytic removal of water contaminants for ecological systems has become
Environmental Remediation under essential in the past few decades. Consequently, for commercialization, cost-efficient, earth-abundant
UV-Light. Metals 2022, 12, 733. and easy to synthesize photocatalysts for dye degradation are of urgent need. We have demon-
https://doi.org/10.3390/ strated a simple and feasible approach for fabricating TiO2 –SnO2 nanocomposite photocatalysts via
met12050733 urea-assisted-thermal-decomposition with different mass ratios. The as-synthesized materials were
characterized by different physicochemical techniques. The phase formation and crystallite size were
Academic Editors: Claudio Pistidda
and Mieczyslaw Jurczyk
calculated by using XRD. The STEM, UV-Vis, DRS, HR-TEM and EDS revealed the effective formation
of the heterojunction between TiO2 and SnO2 , and enrichment in the UV-absorption spectrum. All
Received: 17 January 2022 synthesized materials were used for the photocatalytic degradation of methyl orange (MO) under
Accepted: 17 March 2022
UV light. The optimized results of the TiO2 –SnO2 nanocomposite showed excellent photostability
Published: 26 April 2022
and photocatalytic activity over a number of degradation-reaction cycles of methyl-orange (MO) dye
Publisher’s Note: MDPI stays neutral under the illumination of ultraviolet light. In addition, the recent method has great potential to be
with regard to jurisdictional claims in applied as a proficient method for mixed-metal-oxide-nanocomposite synthesis.
published maps and institutional affil-
iations. Keywords: TiO2 –SnO2 ; urea; nanocomposite; combustion; photocatalysis

Copyright: © 2022 by the authors.

1. Introduction
Licensee MDPI, Basel, Switzerland.
This article is an open access article Dyes play a prominent role in modern life, such as in clothes, beauty products, the
distributed under the terms and paper industry, and foods [1]. Dyes are categorized into metal-complex dyes, functional
conditions of the Creative Commons dyes, azo dyes and reactive dyes [2]. They are organic compounds with functional groups
Attribution (CC BY) license (https:// R-N = N-R− , R and R− substituents [3]. The methyl orange is a dye-containing the azo
creativecommons.org/licenses/by/ group, so it is called an azo dye [4,5]. These dye-industry wastes are considered toxic,
4.0/). poisonous and non-biodegradable. Generally, these wastes are discharged into rivers,

Metals 2022, 12, 733. https://doi.org/10.3390/met12050733 https://www.mdpi.com/journal/metals

Metals 2022, 12, 733 2 of 12

hence becoming the cause of serious water pollution [6,7]. In addition, it gives rise to
various problems such as lower sunlight penetration into streams, toxic life for mammals,
fishes and other sea life. Therefore, the main task in the present era is to reduce water
pollution and have safe water for the ecological community. Towards this endeavor, the
degradation of dyes is executed by various methods such as precipitation and adsorption,
which involve oxidase and hydroxylase enzymes [8]. TiO2 nanoparticles are considered
to be the most efficient at reducing organic dyes due to their excellent features such as
low cost, high reactivity and chemical stability [9,10]. Additionally, they exhibit high
photostability, non-toxicity, and greater oxidation strength with good crystallinity, surface
area, and crystallite size, and hence are used as semiconductor photocatalysts for water
and air purification [11–15]. TiO2 is present in the form of allotropes that are categorized
as rutile, brookite and anatase. Amongst these, the anatase phase has more surface area
and a high crystallinity, which increases photoactivity [16,17]. However, the band gap of
TiO2 (~3.2 eV) is quite large, which results in the fast recombination of the exciton and
the lack of visible-light utilization, which in turn hampers its potential applicability as a
photocatalyst at the commercial level. In this case, it is necessary to combine TiO2 with
another semiconductor metal oxide in order to reduce the fast recombination of excitons.
SnO2 semiconductors with a lower bandgap can trap the photogenerated charge carriers
and decrease the recombination rate. SnO2 mixed with TiO2 increases the catalytic activity
due to the generation of an intermediate band gap [18–20]. The photocatalytic efficiency
depends upon the recombination rate of the electron-hole pair coming from the surface-
charge transfer. The semiconductor decreases the recombination rate of the produced charge
carriers, demonstrating the enhancement in photocatalytic activity [21–26]. The extensive
use of the combination of TiO2 /SnO2 as photocatalyst is due to its higher quantum yield.
The effective separation of the electron-hole pair of photoionized compound is because
of the different CB of TiO2 and SnO2 [27–29]. Most of the synthesis techniques for the
preparation of the TiO2 /SnO2 composites are complicated due to the addition of SnO2 ,
which in turn aids in decreasing crystallinity. Therefore, we converted the anatase to the
rutile phase by using the combustion method with the suitable condition. The complex
metal oxides such as TiO2 /SnO2 photocatalyst were prepared by using the stearic-acid
method [30,31].
Herein, we reported the convenient strategy for the preparation of TiO2 /SnO2 nanocom-
posites through combustion method, which resulted in an anatase structure, high surface
area, high crystallinity and excellent photocatalytic activity. In the present study, the
TiO2 /SnO2 nanocomposite showed enhanced photocatalytic activity towards the MO-dye
degradation under ultraviolet-light irradiation.

2. Experimental
2.1. Materials
Stannous chloride (SnCl4 ·H2O) (Merck, Mumbai, India), Titanium oxysulphate (TiOSO4 ·H2O)
(Sigma Aldrich, Mumbai, India), Urea (NH2 CONH2 ) purchased from Merck (Mumbai,
India), and Methyl Orange (Molychem, Mumbai, India) of analytical grade were used.

2.2. Synthesis of SnO2 , TiO2 Nanoparticles (NPs) and TiO2 –SnO2 Nanocomposite
The SnO2 and TiO2 NPs were prepared following the urea-assisted combustion method
as per our previous report [32]. The as-obtained TiO2 and SnO2 were represented as TU
and SU, respectively. For the preparation of TiO2 –SnO2 nanocomposites, the SnCl4 ·H2 O,
TiOSO4 ·H2 O and NH2 CONH2 were grounded into fine powders in mortar and pestle and
subjected to heat treatment at high temperature (600 ◦ C) with a heating rate of 15 ◦ C/min
for 3 h. The synthesized photocatalyst was washed away by utilizing the distilled water
(DW) then dried in an oven at 110 ◦ C. The fine powder was obtained by grinding this
final product. Photocatalyst TiO2 –SnO2 nanocomposites were obtained with different
mass ratios of TiOSO4 ·H2 O:SnCl4 ·H2 O (0.950:0.050, 0.900:0.100, 0.850:0.150, 0.800:0.200,
Metals 2022, 12, 733 3 of 12

0.750:0.250, and 0.700:0.300) and denoted as TSU95, TSU90, TSU85, TSU80, TSU75 and
TSU70, respectively.

2.3. Structural Characterization

The nanocrystalline structure of as-synthesized SnO2 NPs, TiO2 NPs and TiO2 –SnO2
nanocomposites were studied with the help of XRD with CuKα radiation (λ = 1.5406 Å)
(Pan analytical diffractometer, Almelo, The Netherlands). The morphological features were
analyzed by and scanning electron microscopy (SEM, Hitachi S-4800), transmission electron
microscopy (TEM) (Titan G2 ChemiSTEM Cs Probe, FEI Company, Hillsboro, OR, USA).
The elemental location and chemical composition of a particular selected area were analyzed
with the help of scanning–transmission electron microscopy. The elemental mapping and
X-ray energy-dispersive spectrometer (Titan G2 ChemiSTEM Cs Probe, FEI Company,
Hillsboro, OR, USA) were useful for the analysis of chemical composition and elemental
location in the particular area. The absorption of light by the photocatalyst was studied with
the help of diffuse reflectance spectra (DRS) and UV-Vis’s spectrophotometer (LABINDIA
Analytical UV-3092, Shimadzu, Model-UV-3600, Kyoto, Japan). The spectrofluorometer
(JASCO, Model FP.750, Tokyo, Japan) was used for the identification of photoluminescence
spectra (PL) of various synthesized materials.

2.4. Photocatalytic Degradation of Methyl Orange (MO) Dye

The photocatalytic activity of as-prepared samples (TU, SU, TSU95, TSU90, TSU85,
TSU80, TSU75 and TSU70) were measured under UV-light irradiation. In this experiment,
0.1 gm catalyst was mixed with 100 mL of 20 ppm aqueous MO solution. At room tempera-
ture, the reaction mixture was stirred (by using a magnetic stirrer) for half an hour before
light irradiation. This was helpful for the formation of adsorption–desorption methyl-
orange (MO) molecules for the equilibrium on the surface of the catalyst. At a specified
interval of time, 3 mL solution was withdrawn. Quantitative determination of MO was per-
formed by measuring the intensity of absorption peak using a UV-Vis spectrophotometer.
For ultraviolet-light irradiation, Philips lamp HPL-N (250 W, Amsterdam, The Netherlands)
was used as a light source. The UV-Vis spectrophotometer (Shimadzu, Model-UV-3600)
was used for absorbance measurement of MO, and it was measured at 464 nm. In each
run, distilled water was used for washing the separated photocatalyst. For monitoring MO
recyclability, the washed photocatalyst sample was added to a fresh solution of methyl
orange for the next cycle, and the absorbance of the MO was measured.

3. Results and Discussion

3.1. XRD Analysis
Figure 1 shows the XRD pattern of the as-synthesized photocatalyst such as TU, SU,
TSU95, TSU90, TSU85, TSU80, TSU75 and TSU70. The TU sample shows peaks at 2θ = 25.3◦ ,
37.7◦ , 48.0◦ , 53.9◦ , 55.1◦ , 62.6◦ , 68.8◦ , 70.3◦ , and 75.1◦ that resemble the (hkl) planes of (101),
(004), (200), (105), (211), (204), (116), (220), and (215), respectively. The observed peak is
related to the anatase phase of TiO2 (JCPDS 21-1272) [32]. Furthermore, the characteristics
peaks of SnO2 (SU) appear at 26.4◦ , 33.7◦ , 37.8◦ , 51.6◦ and 61.7◦ , which are indexed to the
(hkl) planes of (110), (101), (200), (220) and (002), respectively. The SU shows the rutile
tetragonal structure of SnO2 , and it is well matched with the JCPDS card number 77-0452.
Metals
Metals2022,
2022,12,
12,x733
FOR PEER REVIEW 5 4ofof13
12

Figure
Figure1.1.XRD
XRDpatterns
patternsofofpure
pureTiO
TiO22(TU),
(TU),pure
pureSnO
SnO22(SU)
(SU)and
andTiO
TiO2–SnO 2 nanocomposites (TSU95,
2 –SnO2 nanocomposites (TSU95,
TSU90, TSU85, TSU80, TSU75 and TSU70) synthesized by combustion
TSU90, TSU85, TSU80, TSU75 and TSU70) synthesized by combustion method. method.

Table The
1. Composition,
XRD patternStructural
of TSU95andand
Optical parameters
TSU90 of as
does not synthesized
show samples.
any typical diffraction peaks
of Weight
SnO2 due to its
Ratio of minor weight ratio in the nanocomposites. In contrast, in the TSU85,
Precursors
TSU80 and TSU75 nanocomposites, Crystallite Size
the slight Band Gap peaks of SnO2
appearance of characteristic
Sr. No Sample (mg)
in the range of 25–38◦ were observed,(nm) which correspond to the (hkl) planes of (110), (101)
(eV)
4·H2O: SnCl4·H2O)
and(TiOSO
(200). No extra peaks were observed in any of the nanocomposites, which showed the
1 Pure TiO2 (TU) successful coupling
1000 of the anatase TiO14and the tetragonal SnO . Hence 3.22 the formation of
2 2
2 Pure SnO2 (SU) the TiO2 –SnO21000 nanocomposite is confirmed.25.96 3.5
3 TSU95 950:50
The crystallite size (D) of all prepared13.43 3.25 Scherrer’s equation.
composites was studied by applying
4 TSU90 900:100 14.05 0.9λ 3.23
D= (1)
5 TSU85 850:150 13.5 β cos θ 3.25
6 TSU80 where the wavelength
800:200 of the X-ray is λ,13.75 θ is the angle of diffraction and3.03β is the full width at
7 TSU75 half maximum (FWHM).
750:250 The diffraction
13.78peak present at the (101) plane
3 of all the samples
8 TSU70 was used for calculating
700:300 the crystallite size.
13.77 The crystallite size of the TU,
3 SU, TSU95, TSU90,
TSU85, TSU80, TSU75 and TSU70 samples was observed to be 14, 25.96, 13.43, 14.05, 13.5,
Metals 2022, 12, 733 5 of 12

13.75, 13.78, and 13.77 nm, respectively. The chemical composition, structural and optical
parameters of the as-synthesized samples are summarized in Table 1. TiO2 is the major
component of the TiO2 –SnO2 nanocomposite. When the concentration of Ti is increased
in the source precursor, it can effectively prevent the accumulation of Sn, leading to the
high dispersion of Ti and Sn, which prevents the agglomeration and particle growth. As a
result, relatively small SnO2 –TiO2 nanocomposites can be formed and the nanocomposites
display a high surface area which is beneficial for catalytic application [33,34].

Table 1. Composition, Structural and Optical parameters of as synthesized samples.

Weight Ratio of Precursors (mg)

Sr. No Sample Crystallite Size (nm) Band Gap (eV)
(TiOSO4 ·H2 O:SnCl4 ·H2 O)
1 Pure TiO2 (TU) 1000 14 3.22
2 Pure SnO2 (SU) 1000 25.96 3.5
3 TSU95 950:50 13.43 3.25
4 TSU90 900:100 14.05 3.23
5 TSU85 850:150 13.5 3.25
6 TSU80 800:200 13.75 3.03
7 TSU75 750:250 13.78 3
8 TSU70 700:300 13.77 3

3.2. Morphological and Structure Analysis of TiO2 –SnO2 Nanocomposite

The structure and morphology of the as-synthesized TiO2 –SnO2 nanocomposites
were analyzed by using HRTEM, EDX, SEM and STEM. Figure 2a–f represents the SEM
images of the TSU95, TSU90, TSU85, TSU80, TSU75 and TSU70 nanocomposite at different
magnifications. Figure 2d (TSU80 sample) shows well-aggregated, composed and porous
nanoparticles (NPs) of SnO2 and TiO2 with sizes of 10–30 nm. The interfacial interaction
and production of the heterojunction between SnO2 and TiO2 NPs contained spherical-
shaped NPs.

Figure 2. SEM images of as-synthesized TiO2 –SnO2 nanocomposites (a) TSU95, (b) TSU90, (c) TSU85,
(d) TSU80, (e) TSU75 and (f) TSU70.
Metals 2022, 12, 733 6 of 12

Figure 3a–d show the TEM images of the TSU80 sample recorded at different mag-
nifications. Figure 3a shows a low-resolution TEM image of the TSU80 sample. From
Figure 3b, it can be seen that the material has interconnected, porous, aggregated, and
spherical NPs with sizes of 10–30 nm. Figure 3d depicts the high-resolution TEM image of
the TSU80 sample. The crystallographic planes of SnO2 show the interplanar distance of
0.26 nm (101) and 0.34 nm (110), respectively. On the other hand, the interplanar distance
0.356 nm was observed for TiO2 , which corresponds to the crystallographic plane (101) and
is in good agreement with the XRD data. Furthermore, Figure 3e–h shows the elemental
mapping that confirms the uniform distribution of Ti, Sn and O elements throughout the
nanocomposite. They also show that the SnO2 nanoparticles are uniformly spread over
the surface of the TiO2 nanostructure, which reveals the coupling of TiO2 –SnO2 . The SEM
and TEM and images of the TSU80 sample reveal no separate boundary between the SnO2
and TiO2 phase because of the identical morphology and structure of the TiO2 NPs and
SnO2 NPs.

Figure 3. (a,b) TEM images of sample TSU80 at different magnification, (c,d) HRTEM of the TiO2 –
SnO2 heterojunction region (e) HAADF image and (f–h) elemental mapping of TSU80 nanocomposite.

3.3. Optical Properties

The photocatalytic activity mainly depends on the absorption of light and its wave-
length. Figure 4a shows the UV-Vis diffuse reflectance spectra of the TU, SU, TSU95, TSU90,
TSU85, TSU80, TSU75 and TSU70 samples. From the Figure 4a, the remarkable absorption
peaks can be observed. The optimized nanocomposites of the TSU80 sample show higher
absorption in terms of UV and visible regions, which may easily be due to transferring the
electron from the valence band (VB) to the conduction band (CB). Band-gap energies were
calculated using the following equation
αhν = A(hν − Eg)n (2)
where α is the absorption coefficient, A is a constant related to the effective mass of the
electrons and holes, Eg is the energy gap and n is a constant related to the type of optical
transition; n = 2 for indirect transition and n = 1/2 for the direct transition.
The estimated Eg values from Tauc plots (Figure 4b) were found to be 3.22, 3.5, 3.25,
3.23, 3.25, 3.03 and 3 eV for TU, SU, TSU95, TSU90, TSU85, TSU80 and TSU75, respectively.
The band-gap energy was reduced upon the combination of SnO2 with TiO2 due to the
intimate interfacial interaction [33,35].
Metals 2022, 12, 733 7 of 12

Figure 4. (a) UV-Vis diffuse reflectance spectra and (b) Tauc plot of TU, SU, TSU95, TSU90, TSU85,
TSU80 and TSU75.

3.4. PL Spectra
Photoluminescence (PL) spectra were acquired to gain more insights into charge-
carrier separation. The PL spectra of photocatalysts (TU, TSU95, TSU90, TSU85, TSU80,
TSU75 and TSU70) were measured at the excitation wavelength of 295 nm for TiO2 and
TiO2 –SnO2 nanocomposite at room temperature as shown in Figure 5. The PL spectra
depicts the two broad emission peaks centered at 410 and 470 nm, which are attributed
to band-edge emission and oxygen vacancies, respectively. When the TiO2 –SnO2 het-
erojunction was formed, the PL intensity of the TSU80 nanocomposite was drastically
reduced, indicating recombination of the charge carrier is suppressed due to interfacial
charge transport from TiO2 and SnO2 was reduced. This is advantageous for the improve-
ment of the photocatalytic performances for the degradation of methyl-orange dyes under
light irradiation.

Figure 5. Photoluminescence (PL) spectra of TU, TSU95, TSU90, TSU85, TSU80 and TSU75.
Metals 2022, 12, 733 8 of 12

3.5. Photocatalytic Degradation of Methyl Orange Applying UV Light

Photocatalyst performances of TU, SU, TSU95, TSU90, TSU85, TSU80, TSU75 and
TSU70 were evaluated for MO-dye degradation under UV-light irradiation. The photo-
catalytic performance was studied by monitoring the absorbance of MO (λmax = 464 nm)
at regular intervals of time using UV-Vis spectroscopy. The degradation efficiency was
estimated by using the following equation [36].
( C0 − C )
D% = (3)
C0
where C0 is the initial concentration and C is the final concentration of methyl orange,
respectively. Figure 6a depicts the relationship between irradiation time and MO-dye
degradation in the presences of UV light by different photocatalysts. The degradation
activity of the as-synthesized photocatalyst for MO degradation was found to be 79.03,
69.5, 84, 88, 92, 98, 95 and 90% for TU, SU, TSU95, TSU90, TSU85, TSU80, TSU75 and
TSU70, for 60 min of light irradiation. The produced TSU80 (~98%) exhibited excellent
photocatalytic activity than the pure-phase TU (79.03%) and SU (69.5%) over 60 min of
light irradiation. This could be attributed to the intimate interfacial connection and the
heterojunction effect between the TiO2 and SnO2 , which could greatly contribute to charge-
carrier (electron/hole) separation and utilization. The degradation of MO was found to
increase with an increase in the incorporation of SnO2 ; however, the excessive inclusion of
SnO2 (>80) had a negative effect on the photocatalytic activity, indicating that TSU80 is an
optimal catalyst. Figure 6b shows the UV-Vis-absorbance spectra for the degradation of
MO dye using TSU80 catalyst.

Figure 6. (a) Photocatalytic degradation of MO using different photocatalysts under UV-light irradia-
tion (b) UV-Vis-absorbance spectra for the degradation of MO dye using TSU80 catalyst.

The photostability and recyclability are vital factors for a photocatalyst to be applied
for commercial applications. Therefore, the stability of the as-synthesized composites was
evaluated under similar conditions by collecting the photocatalyst after measurement and
reuse. As shown in Figure 7, the photocatalytic activity was retained to ~90% after five
successive cycles, demonstrating that these photocatalysts can be used multiple times.
The schematic representation illustrates the charge-transfer pathway on the TiO2 –SnO2
nanocomposite for photocatalytic MO-dye degradation (Scheme 1). Based on the above
discussion and band-gap energy of SnO2 (rutile tetrahedral, 3.5 eV) and TiO2 (anatase,
3.2 eV), the TiO2 –SnO2 nanocomposite exhibits type II band alignment [37]. Upon light
irradiation, both SnO2 and TiO2 excited the electrons from the valence band (VB) to the
conduction band (CB) and created photoexcited holes (h+ ) in the VB and electrons (e− )
in the CB. The TiO2 has a higher negative CB than that of SnO2 , which is likely form
heterojunction between the SnO2 and TiO2 . The electrostatic field generated at the interfaces
of TiO2 –SnO2 provides a driving force for the transfer of an electron from the CB of TiO2
Metals 2022, 12, 733 9 of 12

to the CB of SnO2 , as the CBM of TiO2 is more negative than that of SnO2 . Meanwhile,
the photogenerated holes (h+ ) in the VB of SnO2 transfer into the VB of TiO2 [37]. This
process increases the separation ability and lifespan of the induced electron-hole pairs. The
formed charge carriers then migrate to the surface of SnO2 , capturing molecular oxygen
that forms superoxide radicals (•O2 − ). Similarly, holes (h+ ) in the VB of TiO2 oxidize the
H2 O, thereby producing hydroxyl radicals (•OH). These •OH and •O2 − radicals act as
strong oxidizing agents towards the degradation of methyl orange in wastewater at an
impressive reaction rate.

Figure 7. Reusability of TSU80 catalyst for degradation of MO dye under UV light irradiation.

Scheme 1. Schematic representation illustrating the charge-transfer pathway of TiO2 /SnO2 (TSU80)
nanocomposite for MO degradation under UV light irradiation.
Metals 2022, 12, 733 10 of 12

From these results, it is evident that MO-dye degradation directly depends upon the
dosage of Sn (IV). The Sn (IV) incorporation can efficiently increase the rate of photocatalytic
reaction in the TiO2 /SnO2 nanocomposite. The enhancement of photocatalytic activity
depends on several factors. (i) The number of holes and photogenerated electrons are rela-
tively low in pure TiO2 due to a higher recombination rate, therefore the photodegradation
of methyl orange requires more time. In the case of TiO2 /SnO2 , the degradation of MO
was high due to due to increasing the separation of photogenerated holes and electrons.
(ii) The calcination at high temperature (600 ◦ C) is beneficial for the separation of holes and
electrons because it greatly produces the photoactive phases such as anatase and rutile.
(iii) The as-synthesized nanocomposite photocatalyst exhibits a higher specific surface area
that can greater increase active-site exposure for the catalytic reaction than TiO2 .

4. Conclusions
In summary, an inexpensive, easy and simple combustion technique was used for
the fabrication of a TiO2 –SnO2 nanocomposite. The as-synthesized TiO2 –SnO2 composite
showed excellent photocatalytic efficiency for methyl-orange degradation under UV light
irradiation compared to pure TiO2 and SnO2 . The enhanced surface area of the nanocom-
posite enables higher MO-dye adsorption while type II band alignment at the interface
leads to a reduction of unwanted electron hole recombination and likely enhance pho-
toactivity (98.4%/60 min). This significant photoactivity was retained even after repeated
use (five cycles), indicating possibility for practical applications in wastewater treatments.
Thus, unique synthesis method developed in this study may lead to innovative designs of
active photocatalysts for environmental remediation applications.

Author Contributions: Writing—original draft, Methodology, S.M.D.; Writing—review & editing,

S.S.P.; Data curation, Formal analysis, S.B.B.; Funding acquisition, S.A. and M.M.G.; Writing—
review & editing, A.M.T.; Validation, N.H.L.; Resources, N.T.N.T.; Formal analysis, data collection,
C.D.K. Conceptualizations, Writing—review & editing, M.S.T.; Supervision, Investigation S.M.K.
Supervision, Project administration. S.R.B. All authors have read and agreed to the published version
of the manuscript.
Funding: This research was funded by Researchers Supporting Program (TUMA-Project-2021-2),
AlMaarefa University, Riyadh, Saudi Arabia.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: The authors deeply acknowledge the Researchers Supporting Program (TUMA-
Project-2021-2), AlMaarefa University, Riyadh, Saudi Arabia for supporting steps of this work.
Conflicts of Interest: The authors declare that they have no known competing financial interest or
personal relationships that could have appeared to influence the work reported in this paper.

References
1. Aspland, J.R. Textile Dyeing and Coloration; AATCC: Research Triangle Park, NC, USA, 1997.
2. Mahmood, A.; Khan, S.U.-D.; Rana, U.A. Theoretical designing of novel heterocyclic azo dyes for dye sensitized solar cells.
J. Comput. Electron. 2014, 13, 1033–1041. [CrossRef]
3. Sha, Y.; Mathew, I.; Cui, Q.; Clay, M.; Gao, F.; Zhang, X.J.; Gu, Z. Rapid degradation of azo dye methyl orange using hollow cobalt
nanoparticles. Chemosphere 2016, 144, 1530–1535. [CrossRef] [PubMed]
4. Cherrak, R.; Hadjel, M.; Benderdouche, N. Heterogenous Photocatalysis Treatement of Azo Dye Methyl Orange by Nano
Composite TiO2 /Diatomite. Orient. J. Chem. 2015, 31, 1611–1620. [CrossRef]
5. Devi, L.G.; Reddy, K.M. Enhanced photocatalytic activity of silver metallized TiO2 particles in the degradation of an azo dye
methyl orange: Characterization and activity at different pH values. Appl. Surf. Sci. 2010, 256, 3116–3121. [CrossRef]
6. Zhou, M.; Lou, X.W.; Xie, Y. Two-dimensional nanosheets for photoelectrochemical water splitting: Possibilities and opportunities.
Sci. Direct 2013, 8, 598–618. [CrossRef]
7. Zulfiqar, M.; Sufian, S.; Bahadar, A.; Lashari, N.; Rabat, N.E.; Mansor, N. Surface-fluorination of TiO2 photocatalysts for
remediation of water pollution: A review. J. Clean. Prod. 2021, 317, 128354. [CrossRef]
Metals 2022, 12, 733 11 of 12

8. Kumar, S.S.; Muruganandham, T.; Jaabir, M.S.M. Photocatalytic Degradation of Methyl Orange using TiO2 /SnO2 Binary Nano
Composite. Int. J. Curr. Microbiol. App. Sci. 2014, 3, 514–522. [CrossRef]
9. Schneider, J.; Matsuoka, M.; Takeuchi, M.; Zhang, J.; Horiuchi, Y.; Anpo, M.; Bahnemann, D.W. Understanding TiO2 Photocatalysis:
Mechanisms and Materials. Chem. Rev. 2014, 114, 9919–9986. [CrossRef]
10. Lee, S.-Y.; Park, S.-J. TiO2 photocatalyst for water treatment applications. J. Ind. Eng. Chem. 2013, 19, 1761–1769. [CrossRef]
11. Al-Salim, N.I.; Bagshaw, S.A.; Bittar, A.; Kemmitt, T.; McQuillan, A.J.; Mills, A.M.; Ryan, M.J. Characterisation and activity of
sol–gel-prepared TiO2 photocatalysts modified with Ca, Sr or Ba ion additives. J. Mater. Chem. 2000, 10, 2358–2363. [CrossRef]
12. Konovalova, T.A.; Kispert, L.D.; Konovalov, V.V. Surface Modification of TiO2 Nanoparticles with Carotenoids. EPR Study.
J. Phys. Chem. B 1999, 103, 4672–4677. [CrossRef]
13. Iwasaki, M.; Hara, M.; Kawada, H.; Tada, H.; Ito, S. Cobalt Ion-Doped TiO2 Photocatalyst Response to Visible Light. J. Colloid
Interface Sci. 2000, 224, 202–204. [CrossRef]
14. Ito, S.; Inoue, S.; Kawada, H.; Hara, M.; Iwasaki, M.; Tada, H. Low-Temperature Synthesis of Nanometer-Sized Crystalline TiO2
Particles and Their Photoinduced Decomposition of Formic Acid. J. Colloid Interface Sci. 1999, 216, 59–64. [CrossRef]
15. Ding, X.-Z.; Liu, X.-H. Synthesis and microstructure control of nanocrystalline titania powders via a sol–gel process. Mater. Sci.
Eng. A 1997, 224, 210–215. [CrossRef]
16. Moon, J.; Takagi, H.; Fujishiro, Y.; Awano, M. Preparation and characterization of the Sb-doped TiO2 photocatalysts. J. Mater. Sci.
2001, 36, 949–955. [CrossRef]
17. Ovenstone, J. Preparation of novel titania photocatalysts with high activity. J. Mater. Sci. 2001, 36, 1325–1329. [CrossRef]
18. Chen, Y.; Liu, B.; Chen, J.; Tian, L.; Huang, L.; Tu, M.; Tan, S. Structure design and photocatalytic properties of one-dimensional
SnO2 -TiO2 composites. Nanoscale Res. Lett. 2015, 10, 200. [CrossRef]
19. Chai, S.; Zhao, G.; Li, P.; Lei, Y.; Zhang, Y.-N.; Li, D. Novel Sieve-Like SnO2 /TiO2 Nanotubes with Integrated Photoelectrocatalysis:
Fabrication and Application for Efficient Toxicity Elimination of Nitrophenol Wastewater. J. Phys. Chem. C 2011, 115, 18261–18269.
[CrossRef]
20. Tada, H.; Hattori, A.; Tokihisa, Y.; Imai, K.; Tohge, N.; Ito, S. A Patterned-TiO2 /SnO2 Bilayer Type Photocatalyst. J. Phys. Chem. B
2000, 104, 4585–4587. [CrossRef]
21. Spanhel, L.; Weller, H.; Henglein, A. Photochemistry of semiconductor colloids. 22. Electron ejection from illuminated cadmium
sulfide into attached titanium and zinc oxide particles. J. Am. Chem. Soc. 1987, 109, 6632–6635. [CrossRef]
22. Gopidas, K.R.; Bohorquez, M.; Kamat, P.V. Photophysical and photochemical aspects of coupled semiconductors: Charge-transfer
processes in colloidal cadmium sulfide-titania and cadmium sulfide-silver(I) iodide systems. J. Phys. Chem. 1990, 94, 6435–6440.
[CrossRef]
23. Serpone, N.; Borgarello, E.; Grätzel, M. Visible light induced generation of hydrogen from H2 S in mixed semiconductor
dispersions; Improved efficiency through inter-particle electron transfer. J. Chem. Soc. Chem. Commun. 1984, 342–344. [CrossRef]
24. Hotchandani, S.; Kamat, P.V. Charge-transfer processes in coupled semiconductor systems. Photochemistry and photoelectro-
chemistry of the colloidal cadmium sulfide-zinc oxide system. J. Phys. Chem. 1992, 96, 6834–6839. [CrossRef]
25. Sato, T.; Masaki, K.; Sato, K.-I.; Fujishiro, Y.; Okuwaki, A. Photocatalytic properties of layered hydrous titanium oxide/CdS–ZnS
nanocomposites incorporating CdS–ZnS into the interlayer. J. Chem. Technol. Biotechnol. 1996, 67, 339–344. [CrossRef]
26. Machida, M.; Ma, X.W.; Taniguchi, H.; Yabunaka, J.-I.; Kijima, T. Pillaring and photocatalytic property of partially substituted
layered titanates, Na2 Ti3-x Mx O7 and K2 Ti4-x Mx O9 (M = Mn, Fe, Co, Ni, Cu). J. Mol. Catal. A Chem. 2000, 155, 131–142.
[CrossRef]
27. Bedja, I.; Kamat, P.V. Capped Semiconductor Colloids. Synthesis and Photoelectrochemical Behavior of TiO2 -Capped
SnO2 Nanocrystallites. J. Phys. Chem. 1995, 99, 9182–9188. [CrossRef]
28. Vinodgopal, K.; Kamat, P.V. Enhanced Rates of Photocatalytic Degradation of an Azo Dye Using SnO2 /TiO2 Coupled Semicon-
ductor Thin Films. Environ. Sci. Technol. 1995, 29, 841–845. [CrossRef] [PubMed]
29. Yang, J.; Li, D.; Wang, X.; Yang, X.; Lu, L. Rapid Synthesis of Nanocrystalline TiO2 /SnO2 Binary Oxides and Their Photoinduced
Decomposition of Methyl Orange. J. Solid State Chem. 2002, 165, 193–198. [CrossRef]
30. Xiong, G.; Wei, G.; Yang, X.; Lu, L.; Wang, X. Characterization and size-dependent magnetic properties of Ba3 Co2 Fe24 O41
nanocrystals synthesized through a sol-gel method. J. Mater. Sci. 2000, 35, 931–936. [CrossRef]
31. Wang, X.; Li, D.; Lu, L.; Wang, X. Synthesis of substituted M- and W-type barium ferrite nanostructured powders by stearic acid
gel method. J. Alloy. Compd. 1996, 237, 45–48. [CrossRef]
32. Deshmukh, S.M.; Tamboli, M.S.; Shaikh, H.; Babar, S.B.; Hiwarale, D.P.; Thate, A.G.; Shaikh, A.F.; Alam, M.A.; Khetre, S.M.;
Bamane, S.R. A Facile Urea-Assisted Thermal Decomposition Process of TiO2 Nanoparticles and Their Photocatalytic Activity.
Coatings 2021, 11, 165. [CrossRef]
33. Yang, J.; Zhang, J.; Zou, B.; Zhang, H.; Wang, J.; Schubert, U.; Rui, Y. Black SnO2 –TiO2 Nanocomposites with High Dispersion for
Photocatalytic and Photovoltalic Applications. ACS Appl. Nano Mater. 2020, 3, 4265–4273. [CrossRef]
34. Jilani, A.; Ansari, M.O.; Rehman, G.U.; Shakoor, M.B.; Hussain, S.Z.; Othman, M.H.D.; Ahmad, S.R.; Dustgeer, M.R.; Alshahrie,
A. Phenol removal and hydrogen production from water: Silver nanoparticles decorated on polyaniline wrapped zinc oxide
nanorods. J. Ind. Eng. Chem. 2022, in press. [CrossRef]
Metals 2022, 12, 733 12 of 12

35. AlAbduljabbar, F.A.; Haider, S.; Ali, F.A.A.; Alghyamah, A.A.; Almasry, W.A.; Patel, R.; Mujtaba, I.M. Efficient Photocatalytic
Degradation of Organic Pollutant in Wastewater by Electrospun Functionally Modified Polyacrylonitrile Nanofibers Membrane
Anchoring TiO2 Nanostructured. Membranes 2021, 11, 785. [CrossRef] [PubMed]
36. Jilani, A.; Rehman, G.U.; Ansari, M.O.; Othman, M.H.D.; Hussain, S.Z.; Dustgeer, M.R.; Darwesh, R. Sulfonated polyaniline-
encapsulated graphene@graphitic carbon nitride nanocomposites for significantly enhanced photocatalytic degradation of phenol:
A mechanistic study. New J. Chem. 2020, 44, 19570–19580. [CrossRef]
37. Wang, C.; Shao, C.; Zhang, X.; Liu, Y. SnO2 Nanostructures-TiO2 Nanofibers Heterostructures: Controlled Fabrication and High
Photocatalytic Properties. Inorg. Chem. 2009, 48, 7261–7268. [CrossRef] [PubMed]