crystals

Article
Investigation of TiO2 Nanoparticles Synthesized by Sol-Gel
Method for Effectual Photodegradation, Oxidation and
Reduction Reaction
Mohamad M. Ahmad 1, * , Shehla Mushtaq 2 , Hassan S. Al Qahtani 3 , A. Sedky 4 and Mir Waqas Alam 1, *

1 Department of Physics, College of Science, King Faisal University, P.O. Box 400, Al-Ahsa 31982, Saudi Arabia
2 School of Natural Sciences, National University of Sciences and Technology, Islamabad 44000, Pakistan;
shehla.mushtaq@sns.nust.edu.pk
3 EXPEC Advanced Research Centre, Saudi Aramco, Dhahran 31311, Saudi Arabia;
Hassan.alqahtani.2@aramco.com
4 Department of Physics, Faculty of Science, Assiut University, Assiut 71516, Egypt; sedky1@aun.edu.eg
* Correspondence: mmohamad@kfu.edu.sa (M.M.A.); wmir@kfu.edu.sa (M.W.A.)

Abstract: Metal oxide titanium dioxide (TiO2 ) nanoparticles were synthesized by using a simple and
economical sol-gel method. The prepared nanoparticles were used to evaluate methylene blue dye
degradation and as catalysts in the oxidation of benzaldehyde. The crystallite size of the titanium
dioxide nanoparticle was 18.3 nm, which was confirmed by X-ray diffraction analysis. The spherical
morphology was confirmed by scanning electron microscopy (SEM), and the elemental composition
of the nanoparticle was found by energy dispersive X-ray (EDAX) analysis. The anatase form of the





 nanoparticle was confirmed by the bandgap 3.2 eV, which was measured using UV–DRS analysis.
Citation: Ahmad, M.M.; Mushtaq, S.;
The bond between metal and oxygen was confirmed by the peaks at 485 and 606 cm–1 analyzed by
Al Qahtani, H.S.; Sedky, A.; Fourier transform infrared analysis (FTIR). The efficiency of the catalyst in dye degradation was
Alam, M.W. Investigation of TiO2 60.08, 68.38, and 80.89% with respect to 50, 75, and 100 mg catalyst weight. The yield % of benzoic
Nanoparticles Synthesized by Sol-Gel acid was 94%, and the reduction efficiency against 4-nitrophenol was 98.44%.
Method for Effectual
Photodegradation, Oxidation and Keywords: benzaldehyde; degradation; metal oxide; methylene blue; nanoparticle; nitrophenol
Reduction Reaction. Crystals 2021, 11,
1456. https://doi.org/10.3390/
cryst11121456

1. Introduction
Academic Editor: Yongsheng Han
In the present era, nanotechnology and nanomaterials play significant roles in many fields,
with environmental applications, energy storage devices, and biological applications [1,2].
Received: 7 November 2021
Accepted: 24 November 2021
Nanomaterials possess unique optical, mechanical, and electrical properties due to
Published: 25 November 2021
their size, shape, stability, chemical composition, crystal structure, surface area, etc. Metal
oxides such as TiO2 , MoO3 , WoO3 , CuO, etc. are less toxic in nature and are used in diverse
Publisher’s Note: MDPI stays neutral
applications. Among these, TiO2 is considered a promising candidate for these applications
with regard to jurisdictional claims in
due to its unique properties, such as a wide bandgap. These metal oxide nanoparticles can
published maps and institutional affil- be synthesized via both top-down and bottom-up approaches. Out of numerous synthesis
iations. methods, the sol-gel method, has been verified as a superior route to control the bulk and
surface properties of the oxides at low temperature [3–5]. The sol-gel system is an efficient
and inexpensive technique used in nanoparticle fabrication. This method yields high crystal
oxides by allowing regulation of nanoparticles’ size and surface morphology, in addition to
Copyright: © 2021 by the authors.
phase arrangement in diverse concentration precursors, and it is simple to perform [6].
Licensee MDPI, Basel, Switzerland.
With increased industrialization and urbanization, water pollution has increased. Due
This article is an open access article
to water pollution, humans are affected by diseases, such as cholera, diarrhea, and hepatitis.
distributed under the terms and Organic dyes are also a major constituent present in polluted water, discharged from the
conditions of the Creative Commons textile, food, and cosmetic industries. Among the discharged organic dyes, methylene
Attribution (CC BY) license (https:// blue (MB) is considered one of the most toxic, causing eye irritation, vomiting, nausea,
creativecommons.org/licenses/by/ and confusion [7]. Therefore, it is important to discover a suitable material to remove this
4.0/). harmful dye from polluted water [8,9]. Numerous methods can be employed to remove

Crystals 2021, 11, 1456. https://doi.org/10.3390/cryst11121456 https://www.mdpi.com/journal/crystals

Crystals 2021, 11, 1456 2 of 16

organic pollutants present in the water, such as adsorption, photodegradation, flocculation,

coagulation, and electrocoagulation [10,11]. Of these methods, photocatalytic degradation
is an efficient method as the nanocatalyst oxidizes organic compounds into inorganic
matter, such as CO2 and H2 O without any intermediate pollutants [12].
Oxidation of benzaldehyde to benzoic acid is an important process, as benzoic acid is
a valuable chemical and is highly used as a precursor in several other molecules. In ad-
dition to that benzoic acid is highly used in medicine, food, and chemical industries. For
environmental purification, the most familiar oxidation reactions are those that oxidize
organic composites [13,14]. Furthermore, the nanostructure is highly utilized as a cocatalyst
for H2 O oxidation [15,16]. The heterogeneous catalyst offers an opportunity to degrade
organic compounds through either oxidation or reduction reactions. The outcomes show
the usefulness of a broad range of materials in the elimination of phenolic compounds
from water and wastewater. Nitro groups containing pollutants are of major concern, as
they are difficult to reduce due to their toxic behavior. Compounds such as 4-nitro phenol
(4-NP) and are toxic but also anthropogenic and inhibitory in nature, so their reduction
is an issue of major importance. For instance, 4-nitrophenol is a phenolic compound, con-
stituting one nitro group present on the benzene ring diagonally to the hydroxyl group.
Further, 4-NP causes eye irritation and inflammation. It interacts with blood and forms
methemoglobin, which results in methemoglobinemia causing cyanosis, confusion, and
unconsciousness. When ingested, it causes abdominal pain and vomiting. Moreover, 4-NP
and its byproducts are used for the synthesis of herbicides, insecticides, and pesticides
that threaten the environment as well as human beings [17]. Nitrophenols are among the
main organic pollutants in wastewater produced from agricultural and industrial sources.
Therefore, the increase in an efficient and environmentally friendly process to eliminate
them from water is highly significant [18].
Metal oxide nanoparticles, such as iron oxide (Fe3 O4 ), manganese oxide (Mn2 O3 ), copper
oxide (CuO), nickel oxide (NiO), zinc oxide (ZnO), etc., act as photocatalysts, which play a sig-
nificant role in the removal of MB from polluted water [19–21]. For photocatalysis applications,
titanium is highly used, known as the ninth most abundant element present in Earth’s crust.
Since the photoinduced and electrochemically facilitated degradation of HO was reported
by Fujishima and Honda in the 1970s, titanium metal has been considered an attractive com-
pound, which possesses several promising applications in photocatalysis [22,23]. Titanium
dioxide (TiO2 ) exists in three forms—anatase, rutile, and brookite. It also exists in mixed
phases of rutile–anatase, anatase–brookite, and anatase–rutile–brookite. In a mixed phase, the
flow of electrons from the anatase to a lower-energy rutile-trapping site could limit charge
carrier recombination and efficiently establish catalytic hot spots. Only a few brookite reports
have been published due to low photocatalytic activity [24].
Both anatase and rutile have tetragonal structures, and brookite has an orthorhombic
structure. Rutile is the most stable, while anatase and brookite are metastable at ambient
temperature [22,25]. In comparison with rutile, anatase exhibits higher transparency in the
near-ultraviolet spectrum. Many researchers examine the TiO2 nanoparticle (TiO2 NP) due
to its less toxic nature, ease of handling, economical cost, and good resistance to chemical
and photochemical erosion [26]. These properties lead TiO2 NPs to play important roles in
sensors, solar cells, environmental remediation, self-cleaning, and hydrogen gas evolution.
The mobility of the electron is very high in anatase TiO2 , and therefore, it is used as a
photoanode material in dye-sensitized solar cells [27]. A recent statistical analysis showed
that the research publications on the photocatalysis of TiO2 have reached 10,000 each
year since 2000. This proves that this material has broad applications due to its excellent
properties. Due to the surface-to-volume ratio of nanostructured TiO2 , the rate of the
photocatalytic process is highly increased, compared with the bulk [28,29]. Owing to the
redox properties of TiO2 , it is highly used in both oxidation and reduction reactions, such as
oxidation of organic contaminants and reduction of metals and organic pollutants [30,31].
Due to the faster recombination process of the photogenerated electron–electron, pure
TiO2 comprises restrained photocatalytic activities, and during the process, unproductive
Crystals 2021, 11, 1456 3 of 16

energies are released either in the form of photon production or heat [32,33]. In this study,
the TiO2 NP was synthesized by the sol-gel method. The synthesized nanoparticle was
analyzed by UV–DRS spectrophotometry, FTIR spectrophotometry, XRD, SEM, and EDX.
The efficiency of the material was verified in terms of MB dye degradation, conversion of
benzaldehyde to benzoic acid by the oxidation process, and 4-nitrophenol to 4-aminophenol
by the reduction process.

2. Experiment
2.1. Materials
Titanium tetra isopropoxide Ti[(OCH)(CH3 )2 ]4 (97% purity) and glacial acetic acid
(CH3 COOH) (100% purity) were used as precursor materials in TiO2 nanoparticles synthe-
sis. Benzaldehyde (99% purity), hydrogen peroxide (30% purity), and dimethylformamide
(99.5% purity) were used in the oxidation of benzaldehyde to benzoic acid. In addition,
4-Nitrophenol (99.5% purity) and sodium borohydride (NaBH4 ) (96% purity) were used in
the reduction process. Methylene blue dye was chosen as a pollutant for the degradation
process. The materials used for synthesis and application were purchased from Merck.
Double distilled water was used as a solvent during the synthesis and application process.

2.2. Synthesis of TiO2 Nanoparticles

Titanium tetra isopropoxide, glacial acetic acid, and double distilled water were used
to synthesize TiO2 nanoparticles as a starting material. First, 15 mL of acetic acid was
blended with 150 mL of double-distilled water and stirred continuously for 30 min under
0 ◦ C, keeping the titania solution beaker in an ice-containing bowl. Then, 5 mL of titanium
tetra isopropoxide was added drop by drop and stirred vigorously for 5 h. To obtain a clear
solution, the above reaction mixture was ultrasonicated for 30 min, and it was kept in the
dark for up to 24 h without disturbance for the nucleation process. Then, the solution was
kept in a hot air oven at 80 ◦ C for 10 h to obtain a gel. The obtained gel was kept in an oven
at 100 ◦ C until completely dry. The dried material was finely powdered by using a mortar
and pestle and calcinated at 600 ◦ C for 5 h to obtain the white color TiO2 nanoparticles.

2.3. Characterization
The crystallite size, plane, and phase of the TiO2 NPs were assessed using X-ray
diffraction analysis performed by an XRD spectrometer (Rigaku-Tokyo, Japan). Cu Kα was
used to perform the analysis with λ = 1.540 Å, 40 kV, and 30 mA, and D/teX Ultra was
used as a detector. The analysis was recorded in the range of 10–80◦ with the scan rate of
10 ◦ /min. The crystallite size was measured by the Debye–Scherrer equation. The average
particle size and morphology were observed by scanning electron microscopy using Bruker.
The average particle size of the nanoparticle was calculated using ImageJ software. The
elemental composition, such as atomic and weight percentage, was identified by EDX
analysis. The functional group present in the nanoparticle was confirmed by FTIR analysis
by a Jasco spectrophotometer, and KBr was used as the standard for the preparation of
the pellet. The analysis was recorded in the range from 4000 to 400 cm−1 . The optical
property of the nanoparticle was analyzed by a UV-2600 ISR 2600 PLUS spectrophotometer,
Shimadzu, Japan. The UV–DRS analysis was recorded in the range of 200–800 nm.

2.4. Photocatalytic Degradation Study

The photocatalytic degradation of MB was performed by using TiO2 NPs as an ef-
fective catalyst. The degradation study was carried out in a batch reactor system with an
open rectangular tray made of borosilicate glass. The tray consisted of 250 mL of a known
concentration (100 µM) of dye solution with a known weight of the catalyst. The pH of the
solution was maintained at 7 ± 0.1. Then, it was stirred with medium rotation per minute
(rpm) for 30 min in the dark to attain adsorption–desorption equilibrium. The absorbance
of the dye solution was measured at 665 nm using UV-Vis spectrophotometry before the
degradation process. Then, the degradation study was performed under direct sunlight
 tive catalyst. The degradation study was carried out in a batch reactor system with an
open rectangular tray made of borosilicate glass. The tray consisted of 250 mL of a known
concentration (100 µM) of dye solution with a known weight of the catalyst. The pH of
the solution was maintained at 7 ± 0.1. Then, it was stirred with medium rotation per mi-
Crystals 2021, 11, 1456 nute (rpm) for 30 min in the dark to attain adsorption–desorption equilibrium. The 4 ofab-
16
sorbance of the dye solution was measured at 665 nm using UV–Vis spectrophotometry
before the degradation process. Then, the degradation study was performed under direct
sunlight irradiation. The intensity of the sunlight irradiation was measured frequently us-
irradiation. The intensity
ing a flux meter, of the
and it was sunlight
observed irradiation
to be was of
in the range measured
820–830 frequently using asolu-
lx. The degraded flux
meter, and it was observed to be in the range of 820–830 lx. The degraded solution
tion was collected at particular time intervals, and the collected solution underwent an was
collected
absorbanceat particular time intervals,
study to calculate and theofcollected
the efficiency solution underwent an absorbance
the catalyst.
study to calculate the efficiency of the catalyst.
2.5. Oxidation of Benzaldehyde to Benzoic Acid
2.5. Oxidation of Benzaldehyde to Benzoic Acid
The oxidation reaction of benzaldehyde to benzoic acid was performed at room tem-
The oxidation reaction of benzaldehyde to benzoic acid was performed at room
perature using TiO2 NPs as an effective catalyst. For the oxidation study, a 5 mL benzal-
temperature using TiO2 NPs as an effective catalyst. For the oxidation study, a 5 mL
dehyde solution was taken as a precursor material, and 10 mg of catalyst was added to
benzaldehyde solution was taken as a precursor material, and 10 mg of catalyst was added
the precursor. This reaction mixture was continuously stirred for 3 h at 60 ± 5 °C. To this,
to the precursor. This reaction mixture was continuously stirred for 3 h at 60 ± 5 ◦ C. To this,
12.5 mL
12.5 mL of
of hydrogen
hydrogen peroxide
peroxide was
was added
added drop
drop wise,
wise, which
which acted
acted as
as an
an oxidizing
oxidizing agent.
agent.
Then, the above reaction mixture was stirred for 3 h. After completion of the
Then, the above reaction mixture was stirred for 3 h. After completion of the reaction,reaction, the
reaction
the mixture
reaction waswas
mixture cooled, filtered,
cooled, washed,
filtered, andand
washed, dried. TheThe
dried. obtained
obtainedmaterial waswas
material re-
crystallized using dimethylformamide. The recrystallized product was taken
recrystallized using dimethylformamide. The recrystallized product was taken as a final as a final
product,and
product, andititwas
wasweighed
weighedaccurately.
accurately.Scheme
Scheme 1 shows
1 shows thethe oxidation
oxidation of benzaldehyde
of benzaldehyde to
to benzoic acid in the presence of TiO 2 NPs as a catalyst.
benzoic acid in the presence of TiO NPs as a catalyst.
2

Scheme 1.
Scheme 1. Oxidation
Oxidation of
of benzaldehyde
benzaldehyde to
to benzoic
benzoic acid.
acid.

2.6.
2.6. Reduction
Reduction ofof 4-Nitrophenol
4-Nitrophenol toto 4-Aminophenol
4-Aminophenol
The
The TiO nanoparticle was
TiO22 nanoparticle wasused usedas asaacatalyst
catalystininthe theconversion
conversionofof4-Nitrophenol
4-Nitrophenol toto
4-
4-Aminophenol (reduction
Aminophenol (reduction reaction)
reaction) with
with NaBH
NaBH 4 as4 aas a reducing
reducing agent,
agent, andand the reaction
the reaction was
was achieved
achieved at room
at room temperature.
temperature. In total,
In total, 5 mmol 5 mmol of 4-nitrophenol
of 4-nitrophenol was dissolved
was dissolved usingusing
dou-
double distilled water in a 100 mL standard flask. At the same time,
ble distilled water in a 100 mL standard flask. At the same time, 0.001 mmol of NaBH 0.001 mmol of NaBH
4 was
4
was dissolved
dissolved in 4 in
mL4 of
mLdistilled
of distilled
water. water.
Next,Next,
20 mL 20 of
mLprepared
of prepared 4-nitrophenol
4-nitrophenol solution
solution and
and sodium
sodium borohydride
borohydride solution
solution werewere added
added to to
a a100
100mL mLbeaker.
beaker.Both
Both the
the solutions
solutions were
were
stirred
stirred for 15 min constantly. To the above reaction mixture, 0.5 mg of catalyst was
for 15 min constantly. To the above reaction mixture, 0.5 mg of catalyst was added,
added,
and
and using
usingthe
themagnetic
magneticstirrer,
stirrer,the
thesolution
solutionwas was stirred
stirredforfor
5 min. The optical
5 minutes. densitydensity
The optical values
were recorded using UV-Vis spectrophotometry for every 1-minute
values were recorded using UV–Vis spectrophotometry for every 1-minute time interval time interval for the
above reaction mixture.
for the above reaction mixture.
3. Results and Discussion
3.1. XRD Analysis
Figure 1 shows the XRD pattern of TiO2 NPs. From the XRD analysis (Rigaku, Tokyo
Japan), the 2θ values were observed at 25.33, 36.01, 37.90, 48.06, 53.96, 55.06, 62.70, 69.01,
and 70.41◦ with respect to the planes (101), (103), (004), (200), (105), (211), (204), (116), and
(220). The diffraction peaks showed that the formed nanoparticles exhibited anatase phase,
which was confirmed by the JCPDS card No. 84-1285. The average crystalline size of the
TiO2 nanoparticles was calculated using Debye–Scherrer Equation (1) and was 10.88 nm.

Kλ
D= (1)
βcosθ

where K is constant, λ = wavelength of X-rays, and β Full width at half maximum (FWHM).
 nm.

𝐾𝜆
𝐷= (1)
𝛽𝑐𝑜𝑠𝜃
Crystals 2021, 11, 1456 5 of 16
where K is constant, 𝜆 = wavelength of X-rays, and 𝛽 Full width at half maximum
(FWHM).

Figure 1.
Figure 1. XRD analysis of TiO
TiO22 nanoparticles.

The (101)
(101) plane
plane of
of anatase
anatase TiO
TiO22 was
was represented
represented by by the
the strongest
strongest diffraction
diffraction peak
peak
situated at 25.33 ◦ . The peaks other than 53.96 and 55.06◦ are accountable to the anatase
25.33°. 53.96 and 55.06° are accountable to the anatase
structure, ◦
structure, and
and 53.96
53.96 and
and 55.06
55.06° are
are responsible
responsible for
for the
the rutile
rutile structure.
structure. This
This suggests
suggests that
that
the
the major crystal phase present in the TiO22 nanoparticles was anatase, and some
major crystal phase present in the TiO nanoparticles was anatase, and some rutile
rutile
phases
phases were
were present
present inin the
the synthesized
synthesized sample
sample with
with minimum
minimum quantity.
quantity. From
From thethe XRD,
XRD,
the
the broad
broad peaks
peaks displayed
displayed thatthat the
the particles
particles were
were nanometer
nanometer size. size. These
These results
results are
are in
in
good agreement with the previous investigation by Liu et al. [34]. Dubey et al.
good agreement with the previous investigation by Liu et al. [34]. Dubey et al. synthesized synthesized
TiO
TiO22 NPs,
NPs, which
which displayed
displayed anatase
anatase phase
phase with
with main
main diffraction
diffraction peaks
peaks at
at 25
25 and
and 48,
48, with
with
no impurities present in the sample. This suggested that the TiO NPs
no impurities present in the sample. This suggested that the TiO22 NPs had a tetragonalhad a tetragonal
anatase
anatase structure
structure with
with trigonal
trigonal planar
planar and
and octahedral
octahedralgeometry
geometry[35]. [35].
3.2. SEM–EDX Analysis
The morphology of the TiO2 NPs was identified as spherical and rod with slight
agglomeration. The average particle size of the TiO2 NPs was 121 nm. Figure 2a,b show the
SEM analysis (Bruker, Karlsruhe, Germany) of TiO2 nanoparticles at 1 µm and 500 nm, re-
spectively. Agglomeration of nanoparticles is due to the adhesion of particles to each other
by weak forces leading to (sub) micron-sized entities and high surface energy. Depend-
ing on the synthesis conditions such as environmental factors, temperature, and surface
chemistry, the nanoparticles tend to form soft or hard agglomerates. Figure 2c shows the
EDX analysis (Bruker, Karlsruhe, Germany) of the TiO2 nanoparticles. Similarly, irregular
and spherical TiO2 NPs with aggregation were obtained by the sol-gel method [36]. Chu
et al. reported that TiO2 NPs displayed regular particles with ammonium fluoride rather
than water, and the as-prepared particles were nanowire in morphology. The material
with water revealed an irregular shape, and the nanoparticles showed mixed morphology
such as rod, sphere, and ellipsoid. According to Chu’s report, ammonium fluoride acted
as a shape-controlling agent, which directed the decomposition of nanowires into regular
particles [37]. The elemental atomic percentage of the Ti, O, and C were 26.4%, 69.48%, and
 Similarly, irregular and spherical TiO2 NPs with aggregation were obtained by the sol-gel
method [36]. Chu et al. reported that TiO2 NPs displayed regular particles with ammo-
nium fluoride rather than water, and the as-prepared particles were nanowire in morphol-
ogy. The material with water revealed an irregular shape, and the nanoparticles showed
mixed morphology such as rod, sphere, and ellipsoid. According to Chu’s report, ammo-
Crystals 2021, 11, 1456 6 of 16
nium fluoride acted as a shape-controlling agent, which directed the decomposition of
nanowires into regular particles [37]. The elemental atomic percentage of the Ti, O, and C
were 26.4%, 69.48%, and 4.12%, respectively. The weight percentage of the Ti, O, and C
were 44.35%,
4.12%, 41.65%,The
respectively. andweight
14%, respectively, which
percentage of was
the Ti, O, determined
and C were through EDX analy-
44.35%, 41.65%, and
sis.
14%, respectively, which was determined through EDX analysis.

Figure
Figure 2.
2. SEM–EDX
SEM–EDX analysis
analysis of
of TiO
TiO22 nanoparticles:
nanoparticles:(a)
(a)SEM
SEMimage
imageat
at11µM;
µM; (b)
(b) 500
500 nm;
nm; (c)
(c) EDX
EDX analysis.
analysis.

3.3. UV–DRS Analysis

The absorption maximum of the TiO2 NP was 386 nm, determined by UV–DRS spec-
trophotometry (ISR 2600 Plus, Shimadzu, Tokyo, Japan). By using the Tauc plot (Equation (2)),
the bandgap energy of the synthesized TiO2 NP was calculated as 3.2 eV, and it was an indirect
bandgap [38]. Figure 3a shows the UV–DRS spectrophotometry and b the Tauc plot. In our
study, the undoped TiO2 NP exhibited absorption at less than 387 nm, as compared with the
previous study of iron, silver, cobalt doped titanium oxide nanoparticles, due to the inherent
bandgap of anatase TiO2 , and it was accredited to the band-to-band transition reported by
Babji et al. [39]. The decreasing particle size increased the bandgap of the material, and the
absorption edge was transferred to higher energy, which was blueshift. In this regard, the
bandgap of the semiconductor material was size dependent [40].

αhµ = Ed (hµ − Eg )1/2 (2)

where α = optical absorption coefficient, hµ = photon energy, Eg = direct band gap, and
Ed = constant.
 [40].
αhµ = Ed(hµ − Eg)1/2
where α = optical absorption coefficient, hµ = photon energy, Eg = direct band g
Crystals 2021, 11, 1456 7 of 16
= constant.

Figure 3. (a) UV–DRS spectrophotometric analysis and (b) Tauc plot of TiO2 nanoparticles.

Figure
3.4.3. (a) Analysis
FTIR UV–DRS spectrophotometric analysis and (b) Tauc plot of TiO2 nanopartic
Figure 4 shows the FTIR analysis (Jasco, Tokyo, Japan) of TiO2 NPs. The Ti-O bond
formation was confirmed by the peak appearing at 485 and 606 cm−1 . This suggests that
3.4. FTIR Analysis
the formed nanoparticle was anatase in structure [41,42]. The band that appeared at
1632 cm−1 4
Figure shows
was thetoFTIR
attributed analysis
the absorption (Jasco,
of water Tokyo,present
molecules, Japan) in the TiO2 NPs. The
of atmosphere,
by nanoparticles during the analysis. The
formation was confirmed by the peak appearing hydroxyl group present
at 485 and 606 cm−1TiO
in the synthesized . This
2 sug
NP was confirmed by the band appearing at 3431 cm−1 . From the analysis, the peak that
the formed nanoparticle
appeared at 1632 and 3431 cmwas anatase
−1 indicates thein structure
hydroxyl group[41,42]. The
was present onband thatofappear
the surface
− 1
the TiO2 nanoparticles. The band appearing at 2919 cm was attributed to the existence of
the asymmetric C-H group in the nanoparticles [43]. According to Samira et al., the absence
of a band around 2900 cm−1 is due to the complete elimination of organic molecules at
high calcination temperatures [44]. The organic molecules present in the nanoparticles
were removed by calcination.
 peared at 1632 and 3431 cm−1 indicates the hydroxyl group was present on the surface o
the TiO2 nanoparticles. The band appearing at 2919 cm−1 was attributed to the existence o
the asymmetric C-H group in the nanoparticles [43]. According to Samira et al., the ab
sence of a band around 2900 cm−1 is due to the complete elimination of organic molecule
Crystals 2021, 11, 1456 8 of 16
at high calcination temperatures [44]. The organic molecules present in the nanoparticle
were removed by calcination.

Figure4.4.FTIR
Figure FTIRspectrophotometric analysis
spectrophotometric of TiO
analysis nanoparticles.
of2 TiO2 nanoparticles.

3.5. Photocatalytic Degradation of the Dye Solution

3.5. Photocatalytic
Effect Degradation of the Dye Solution
of Catalyst Weight
Effect of Catalyst
Metal oxides, suchWeightas CdS, Mn2 O3 , ZnO, ZrO2 , Fe3 O4 , etc., act as better catalysts due
to theirMetal oxides, such asand
remarkable bandgap CdS,high
Mnphotocatalytic
2O3, ZnO, ZrO activity.
2, Fe3OIn this study,
4, etc., act asTiO 2 NPcatalysts
better was du
used as an efficient catalyst in the degradation of MB dye solution
to their remarkable bandgap and high photocatalytic activity. In this study, TiO2 NP wa of known concentration
(100 µM) with different catalyst weights of 50 mg, 75 mg, and 100 mg at pH 7 ± 0.1. The
used as an efficient catalyst in the degradation of MB dye solution of known concentration
efficiency percentage was calculated using Equation (3). The absorption spectrum of the
(100 µM) with different catalyst weights of 50 mg, 75 mg, and 100 mg at pH 7 ± 0.1. Th
degraded solution steadily decreased as the reaction time increased, which may be due
efficiency
to percentage
the degradation of the was calculatedpresent
chromophore using Equation
in MB. The (3). The absorption
efficiency percentage spectrum
of the of th
degraded solution
degradation of MB dye steadily
solutiondecreased
using TiOas the reaction time increased, which may be due to
2 NP was 60.08, 68.38, and 80.89%, with respect
thethe
to degradation
catalyst weights of the 50,chromophore
75, and 100 mg. present in MB. The efficiency
The photodegradation of MB dyepercentage
by TiO2 NP of the deg
radation
is shown in of Figure
MB dye S1 solution using TiOMaterials).
(in Supplementary 2 NP was 60.08, Figure68.38,
5a showsand 80.89%,
the plot of with
timerespect to
vs.
theabsorbance,
catalyst weights Figure50, 5b 75,
showsandthe100plot
mg.ofThe timephotodegradation
vs. % degradation,ofFigure MB dye 5c shows
by TiO2 NP i
the
shownlinear inregression
Figure S1graph with respect to time
(in Supplementary vs. ln (cFigure
Materials). 0 /ct ), and5a Figure
shows5dthe shows
plot the
of time vs
degradation % with respect to the number of cycles. The highest
absorbance, Figure 5b shows the plot of time vs. %2 degradation, Figure 5c shows response can be clearly seenthe linea
at 100 mg with the first run. The correlation coefficient (R ) of the degradation of MB dye with
regression graph with respect to time vs. ln (c0/ct), and Figure 5d shows the degradation
different catalyst weights 50, 75, and 100 mg was 0.7945, 0.9550, and 0.9598, respectively. The
% with
rate constantrespect
(k) fortodegradation
the number of dye
of the cycles. Thewith
solution highest response
different catalystcan be clearly
weights seen at 100
50, 75, and
mgmg
100 withwasthe 15.3first
× 10run. The×correlation
−3 , 19.1 10−3 , and 27.5 coefficient
× 10−3 min(R −1 ,) respectively.
2 of the degradation of MB dye with
The photocatalytic
different catalyst weights 50, 75, and 100 mg was 0.7945, 0.9550,
degradation reaction of MB increased with an increase in catalyst weight, due to the increased and 0.9598, respectively
The rate
number of constant
active sites(k) for degradation
present on the surfaceof of the dye solution
the catalyst. with site
If the active different catalyst
of the catalyst is weight
higher,
50, 75, itandincreases
100 mg thewas
number15.3of photons
× 10 adsorbed,
−3, 19.1 × 10−3, and which
27.5allows
× 10−3amin
higher number of dyeThe pho
−1, respectively.

molecules
tocatalytictodegradation
be mineralized. The absorbance
reaction and % degradation
of MB increased of the dyeinwith
with an increase respect
catalyst to
weight, du
time in presence of different weight catalysts are shown in Supplementary
to the increased number of active sites present on the surface of the catalyst. If the activ Data (Table S1).

Degradation % = ( A0 − At /A0 ) × 100 (3)

where A0 —absorbance at the initial time, and At —absorbance at different time intervals.
 higher number of dye molecules to be mineralized. The absorbance and % degradation of
the dye with respect to time in presence of different weight catalysts are shown in Sup-
plementary Data (Table S1).

Crystals 2021, 11, 1456 Degradation % = (A0 – At/A0) × 100 9 of(3)

16

where A0—absorbance at the initial time, and At—absorbance at different time intervals.

Figure 5. (a) Plot of time vs. absorbance, (b) plot of time vs. % Degradation, (c) linear regression graph of MB degradation
using different catalyst weights, and (d) plot for number of cycles using different catalyst doses vs. % degradation.
Figure 5. (a) Plot of time vs. absorbance, (b) plot of time vs. % Degradation, (c) linear regression graph of MB degradation
using different catalyst weights, and (d) plot for number of cycles using different catalyst doses vs. % degradation.
The photocatalytic activity of TiO2 NPs was enhanced by the spherical morphol-
ogy and small crystallite size. The TiO2 hollow nanofiber showed higher photocatalytic
efficiency at 0.75 g/L and moderate at 1.0 g/L, as reported by Jafri et al. [45]. In this
degradation process, the nanoparticle had higher active sites at the optimum weight of the
catalyst, and there was a gradual decrease in active sites of the nanoparticle as the weight
of the catalyst exceeded the optimum weight. This may be caused by the agglomeration of
the photocatalyst, which led to a decrease in the precise surface area of the nanoparticle,
and owing to the screening effect of a large amount of catalyst, the number of photons
received by the active site was decreased [46,47]. According to Muthee et al., the mixed
anatase–rutile phase acts as a highly active photocatalyst [48]. The recycling and reusability
of the catalyst are important in commercial uses. After the degradation reaction, the catalyst
was collected from the dye solution and washed with double distilled water several times,
and dried in an oven at 80 ◦ C. The collected catalyst was further used for a reusability study.
After two runs, the efficiency of the catalyst decreased, as shown in Supplementary Data
(Table S2). The decrease in the photocatalysis activity could be attributed to the following:
(1) Material losses might occur in the revival step (washing and drying), which would lead
to a lower quantity in the successive cycle, thereby decreasing the surface catalytic activity
and degrading the performance; (2) the properties of nanoparticles such as aggregation
(this effect can reduce the effective surface area and decrease the number of active sites)
might change during the three cycles; (3) the adsorptive catalytic surface activity of the
catalyst gradually decreased because of the obstruction of the pores and the active sites.
Crystals 2021, 11, 1456 10 of 16

The related degradation reaction of MB using nanoparticles as an efficient catalyst is shown

in Table 1 [49–52]. Sarigul et al. synthesized a hybrid amino acid–TiO2 nanoparticle for
photocatalytic activity and compared its efficiency with commercial TiO2 (P25). The amino
acid with TiO2 nanoparticle increased the photocatalytic activity against MB degradation
under visible light, compared with the commercial P25. This is because the hybrid materials
are more stable against both degradation and leaching. Considering the commercial TiO2 ,
which is P25 (Degussa/Evonik/Nippon Aerosol), a highly used commercial photocatalyst,
the degradation time for P25 is 240 min, while our results showed a degradation time of 60
at an even higher concentration [53].

Table 1. Degradation reaction of MB using nanoparticles as an efficient catalyst.

S. No Catalyst Pollutant Reduction % Reference

MB 95%
Methyl orange 94%
1 α-Fe2 O3 49
Bromo green 94%
Methyl red 76%
2 Fe2 O3 /Mn2 O3 MB
MB 89%
Methyl orange 92%
3 NiFe2 O4 51
Bromo green 93%
Methyl red 78%
4 Fe3 O4 /TiO2 MB 97% 52
MB
50 mg catalyst
60.08%
75 mg catalyst
5 TiO2 68.38% Present work
100 mg catalyst
80.89%
4-nitrophenol
98.44%
0.5 mg catalyst

3.6. Oxidation of Benzaldehyde to Benzoic Acid

The oxidation of benzaldehyde to benzoic acid was completed by using TiO2 NPs as a
catalyst. Figure 6a,b show the FTIR spectrum of the oxidation of benzaldehyde to benzoic
acid without and with the catalyst. We performed the conversion of benzaldehyde to
benzoic acid using H2 O2 in the presence of the catalyst, and the same reaction was carried
out without the catalyst using H2 O2 . The characteristic peak appearing at 1696 cm−1 was
attributed to the existence of the C=O stretching vibration. A peak value was observed
at 2863 cm−1 with respect to the –COOH group present in the product, which confirmed
the aldehyde converted to acid. The presence of the C=C aromatic stretching vibration
was confirmed by the peak observed at 1428 cm−1 . The aromatic C-H group was present
in the product, as confirmed with the peaks at 684 and 531 cm−1 . A peak appeared at
925 cm−1 with respect to the presence of the O-H bending vibration in the benzoic acid,
and a peak appeared at 1299 cm−1 corresponding to the C-O stretching vibration. The
characteristic peak that appeared at 1695 cm−1 was attributed to the existence of C=O
stretching vibration. The peak value observed at 2836 cm−1 with respect to the –COOH
group present in the product confirms the aldehyde converted to acid. The presence of
C=C aromatic stretching vibration was confirmed by the peak observed at 1430 cm−1 . The
aromatic C-H group was present in the product was confirmed with the peak 683 and
529 cm−1 . The peak appearing at 927 cm−1 with respect to the presence of O-H bending
vibration in the benzoic acid, together with the peak appearing at 1291 cm−1 , corresponds
to C-O stretching vibration. The time taken for conversion of benzaldehyde to benzoic
acid without and with a catalyst was nine hours and six hours, respectively. From this, we
confirmed that the addition of the catalyst increased the rate of the reaction. The yield of
benzoic acid was measured as 3.18 g. The yield % was calculated by following Equation (4).
 group was present in the product was confirmed with the peak 683 and 529 cm−1. The peak
appearing at 927 cm−1 with respect to the presence of O-H bending vibration in the benzoic
acid, together with the peak appearing at 1291 cm−1, corresponds to C-O stretching vibra-
tion. The time taken for conversion of benzaldehyde to benzoic acid without and with a
Crystals 2021, 11, 1456 catalyst was nine hours and six hours, respectively. From this, we confirmed that the ad-
11 of 16
dition of the catalyst increased the rate of the reaction. The yield of benzoic acid was meas-
ured as 3.18 g. The yield % was calculated by following Equation (4).

Yield (%) = (Actual weight/Theoretical weight) × 100 (4)

The mechanism ) =oxidation
Yieldof(%the (Actual weight/Theoretical weightto
reaction of benzaldehyde ) × 100 acid with hy-
benzoic (4)
drogen
Theperoxide
mechanismas an
of oxidizing agent
the oxidation and TiO
reaction 2 NPs as a catalyst is shown in Figure 7.
of benzaldehyde to benzoic acid with hydro-
The H 2O2 was activated on the surface of the catalyst, which occurred through the reaction
gen peroxide as an oxidizing agent and TiO2 NPs as a catalyst is shown in Figure 7. The
between
H2 O2 was theactivated
H2O2 andon –OHthegroup
surfacepresent
of theincatalyst,
the catalyst.
whichThis reactionthrough
occurred led to the formation
the reaction
of TiO -OOH peroxo surface species. Then, the O-O bond was polarized in the
between the H2 O2 and –OH group present in the catalyst. This reaction led to the formation
2 species,
which
of TiO2led-OOHthe peroxo
nucleophilic
surfacealdehyde
species.toThen,
be attacked
the O-Oby the was
bond hydroxyl group
polarized inand formed
the species,
benzoic
which led acid
theasnucleophilic
a major product [54]. to be attacked by the hydroxyl group and formed
aldehyde
benzoic acid as a major product [54].

Crystals 2021, 11, x FOR PEER REVIEW 12 of 17

Figure 6. FTIR analysis of the oxidation of benzaldehyde to benzoic acid by TiO nanoparticles: (a) without catalyst and
Figure 6. FTIR analysis of the oxidation of benzaldehyde to benzoic acid by TiO22 nanoparticles: (a) without catalyst and
(b) with
(b) with catalyst.
catalyst.

FigureFigure
7. Mechanism of oxidation
7. Mechanism of benzaldehyde
of oxidation to benzoic
of benzaldehyde acid. acid.
to benzoic

3.7. Reduction
3.7. Reduction of 4-Nitrophenol
of 4-Nitrophenol to 4-Aminophenol
to 4-Aminophenol
The catalytic
The catalytic efficiency
efficiency of TiO
of TiO 2 nanoparticles
2 nanoparticles wasstudied
was studied for
for the
thereduction
reduction ofof
4-nitrophenol
4-ni-
trophenol as a pollutant. In this reduction process, 4-nitrophenol was reduced to 4-ami- and
as a pollutant. In this reduction process, 4-nitrophenol was reduced to 4-aminophenol,
this process
nophenol, and thiswas carried
process wasout at room
carried outtemperature. During theDuring
at room temperature. process,
the4-nitrophenol
process, 4- was
changed
nitrophenol wastochanged
phenolate to ion as an intermediate,
phenolate and finally,and
ion as an intermediate, thefinally,
intermediate was changed
the intermedi-
to 4-aminophenol [55]. Figure 8 shows the mechanism of conversion
ate was changed to 4-aminophenol [55]. Figure 8 shows the mechanism of conversion of of 4-nitrophenol to
4-aminophenol by the reduction process. The conversion reaction
4-nitrophenol to 4-aminophenol by the reduction process. The conversion reaction was was completed within
20 min,
completed and 20
within theminutes,
absorption andwas
the recorded
absorption forwas
every 1 minute
recorded for during
every 1the reduction
minute duringprocess.
A sharp peak with high intensity around 400 nm was observed,
the reduction process. A sharp peak with high intensity around 400 nm was observed, which can be accredited to
4-nitrophenol at 0 min, and a broad peak was observed at 300 and
which can be accredited to 4-nitrophenol at 0 minutes, and a broad peak was observed at 230 nm, which can be
300 and 230 nm, which can be accredited to 4-aminophenol at 20 minutes. The TiO2 nano-
particles showed a reduction efficiency of up to 98.44% at the nine-minute interval, and
the R2 value was 0.9492. Figure 9a shows the plot of Time vs. % Reduction, while Figure
9b shows the linear regression coefficient. Table 2 shows the absorbance and % Reduction
 nitrophenol was changed to phenolate ion as an intermediate, and finally, the intermedi-
ate was changed to 4-aminophenol [55]. Figure 8 shows the mechanism of conversion of
4-nitrophenol to 4-aminophenol by the reduction process. The conversion reaction was
completed within 20 minutes, and the absorption was recorded for every 1 minute during
Crystals 2021, 11, 1456 the reduction process. A sharp peak with high intensity around 400 nm was observed, 12 of 16

which can be accredited to 4-nitrophenol at 0 minutes, and a broad peak was observed at
300 and 230 nm, which can be accredited to 4-aminophenol at 20 minutes. The TiO2 nano-
particles showed
accredited a reduction
to 4-aminophenol efficiency
at 20 min. TheofTiO
up to 98.44% at the nine-minute interval, and
2 nanoparticles showed a reduction efficiency
the R
of up to 98.44% at the nine-minute interval, and the Rofvalue
2 value was 0.9492. Figure 9a shows the plot 2 Timewas
vs. 0.9492.
% Reduction, while Figure
Figure 9a shows the
9b shows the linear regression coefficient. Table 2 shows the absorbance and % Reduction
plot of Time vs. % Reduction, while Figure 9b shows the linear regression coefficient. Table 2
with respect
Crystals 2021, 11, x FOR PEER REVIEW
shows to time for
the absorbance and4-nitrophenol reduction.
% Reduction with respect to time for 4-nitrophenol13reduction.
of 17

Table 2. Absorbance and % reduction with respect to time for 4-nitrophenol reduction.

S. No Time (min) Absorbance % Reduction ln(c0/ct)

1 0 2.7234 0 0
2 1 2.1887 19.63 0.0949
3 2 1.4367 47.24 0.2776
4 3 1.0410 61.77 0.4176
5 4 0.8030 70.51 0.5304
6 5 0.5890 78.77 0.6650
7 6 0.3753 86.21 0.8607
8 7 0.2143 92.13 1.1041
9 8 0.1082 96.02 1.4009
Figure108. Mechanism
9 of reduction of
0.0423
4-nitrophenol to 98.44
4-aminophenol. 1.8124
Figure 8. Mechanism of reduction of 4-nitrophenol to 4-aminophenol.

Figure 9.
Figure 9. (a)
(a)plot
plotofof
time vs.vs.
time % reduction and (b)
% reduction andtime
(b)vs. ln (cvs.
time 0/ct) and linear regression.
ln (c0 /ct ) and linear regression.
Crystals 2021, 11, 1456 13 of 16

Table 2. Absorbance and % reduction with respect to time for 4-nitrophenol reduction.

S. No Time (min) Absorbance % Reduction ln (c0 /ct )

1 0 2.7234 0 0
2 1 2.1887 19.63 0.0949
3 2 1.4367 47.24 0.2776
4 3 1.0410 61.77 0.4176
5 4 0.8030 70.51 0.5304
6 5 0.5890 78.77 0.6650
Crystals 2021, 11, x FOR PEER REVIEW 7 6 0.3753 86.21 0.8607 14 of 17
8 7 0.2143 92.13 1.1041
9 8 0.1082 96.02 1.4009
10 9 0.0423 98.44 1.8124
3.8. Reusability Study
The reusability
3.8. Reusability Study of the catalyst is important in industrial aspects. After the completion
of the reaction, the catalyst was separated using a separating funnel. The separated cata-
The reusability of the catalyst is important in industrial aspects. After the completion
lyst was further washed with double distilled water several times to remove the product
of the reaction, the catalyst was separated using a separating funnel. The separated catalyst
and impurities and dried at 80 °C till completely dry. Then, the separated TiO2 NP was
was further washed with double distilled water several times to remove the product and
further used for oxidation reaction to verify the reusability of the catalyst, and the same
impurities and dried at 80 ◦ C till completely dry. Then, the separated TiO2 NP was further
reaction
used was carried
for oxidation out. The
reaction efficiency
to verify of the catalyst
the reusability decreased
of the catalyst,during
and thefive runs,
same 94, 87,
reaction
78, 69, and 64% for benzaldehyde oxidation. Figure 10 shows the yield % of benzoic
was carried out. The efficiency of the catalyst decreased during five runs, 94, 87, 78, 69, and acid
in different cycles. With each cycle, the % yield decreased due to the leaching
64% for benzaldehyde oxidation. Figure 10 shows the yield % of benzoic acid in different of the nano-
particle
cycles. during
With eachthe washing
cycle, and drying
the % yield afterdue
decreased every cycle.
to the Therefore,
leaching of thefor the first cycle,
nanoparticle the
during
efficiency
the washingwas 94%, and
and drying afterthen
everywith
cycle.each cycle, for
Therefore, it decreased until
the first cycle, the64% efficiency
efficiency was
was 94%,
achieved in the fifth cycle.
and then with each cycle, it decreased until 64% efficiency was achieved in the fifth cycle.

Figure10.
Figure 10.Yield
Yield%%ofofbenzoic
benzoicacid
acidinindifferent
differentcycles.
cycles.

4.4.Conclusions
Conclusions
The
Theanatase
anataseTiO 2 NPs
TiO 2 NPswere successfully
were successfullysynthesized by a by
synthesized simple sol-gelsol-gel
a simple method. From
method.
XRD analysis, the formed nanoparticle showed the anatase structure confirmed
From XRD analysis, the formed nanoparticle showed the anatase structure confirmed with JCPDS
card
withNo. 84-1285.
JCPDS card No.The84-1285.
crystallite
Thesize of the synthesized
crystallite nanoparticle
size of the synthesized was 18.3 nm
nanoparticle was with
18.3
spherical morphology. The bandgap (3.2 eV) revealed that the formed
nm with spherical morphology. The bandgap (3.2 eV) revealed that the formed nanopar- nanoparticle was
in anatase
ticle was in form. Theform.
anatase bond The
formation between metal
bond formation andmetal
between oxideandwasoxide
confirmed by FTIR
was confirmed
analysis.
by FTIR The efficiency
analysis. The of degrading
efficiency of the dye solution
degrading decreased
the dye solutionwith the increased
decreased with use
the of
in-
the catalyst in the reusability study. The yield percentage of conversion of benzaldehyde
creased use of the catalyst in the reusability study. The yield percentage of conversion of
to benzoic acid to
benzaldehyde also decreased
benzoic acid with the increased
also decreased withnumber of cycles
the increased for theof
number same reaction.
cycles for the
In
same reaction. In the reduction process, 98.44% of 4-nitrophenol was converted toHence,
the reduction process, 98.44% of 4-nitrophenol was converted to 4-aminophenol. 4-ami-
nophenol. Hence, it was shown that the TiO2 NPs were efficient catalysts in the degrada-
tion of methylene blue, the oxidation of benzaldehyde, and the reduction of 4-nitrophenol.

Supplementary Materials: The following are available online at www.mdpi.com/xxx/s1, Figure S1:
Crystals 2021, 11, 1456 14 of 16

it was shown that the TiO2 NPs were efficient catalysts in the degradation of methylene
blue, the oxidation of benzaldehyde, and the reduction of 4-nitrophenol.

Supplementary Materials: The following are available online at https://www.mdpi.com/article/10

.3390/cryst11121456/s1, Figure S1: Photodegradation of methylene blue dye by TiO2 nanoparticles
for 50 mg, 75 mg and 100 mg; Figure S2: Mechanism of oxidation of benzaldehyde to benzoic acid;
Table S1: Absorbance and % degradation of dye with respect to time in presence of different catalyst
weight; Table S2: Reusability study of photocatalyst.
Author Contributions: Conceptualization, M.W.A. and M.M.A.; methodology, M.M.A., S.M., and
M.W.A.; validation, M.M.A., and M.W.A.; formal analysis, M.M.A., H.S.A.Q., and M.W.A.; investi-
gation, M.M.A., S.M., H.S.A.Q., and M.W.A.; resources, M.M.A., A.S., and M.W.A.; data curation,
S.M., H.S.A.Q.; writing—original draft preparation, M.M.A., S.M., H.S.A.Q., A.S., and M.W.A.;
writing—review and editing, M.M.A., S.M., H.S.A.Q., A.S., and M.W.A.; visualization, M.M.A.,
A.S.; supervision, M.M.A., A.S.; project administration, M.M.A., A.S., and M.W.A.; funding acqui-
sition, M.M.A., A.S., and M.W.A. All authors have read and agreed to the published version of
the manuscript.
Funding: The authors acknowledge the Deanship of Scientific Research at King Faisal University for
financial support under the DSR Annual Project (Grant No. 130153).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Lavacchi, A.; Bellini, M.; Berretti, E.; Chen, Y.; Marchionni, A.; Miller, H.A.; Vizza, F. Titanium dioxide nanomaterials in
electrocatalysis for energy. Curr. Opin. Electrochem. 2021, 28, 100720. [CrossRef]
2. Mesgari, M.; Aalami, A.H.; Sahebkar, A. Antimicrobial activities of chi-tosan/titanium dioxide composites as a biological
nanolayer for food preservation: A review. Int. J. Biol. Macromol. 2021, 176, 530–539. [CrossRef]
3. Manikandan, V.; Elancheran, R.; Revathi, P.; Vanitha, U.; Suganya, P.; Krishnasamy, K. Synthesis, characterization, photocata-lytic
and electrochemical studies of reduced graphene oxide doped nickel oxide nanocomposites. Asian J. Chem. 2021, 33, 411–422.
[CrossRef]
4. Thirugnanasambandham, K.; Sivakumar, V. Modeling and optimization of treatment of milk industry wastewater using chitosan–
zinc oxide nanocomposite. Desalination Water Treat. 2015, 57, 18630–18638. [CrossRef]
5. Avinash, B.; Ravikumar, C.R.; Kumar, M.R.A.; Santosh, M.S.; Pratapkumar, C.; Nagaswarupa, H.P.; Murthy, H.C.A.; Deshmukh, V.V.;
Bhatt, A.S.; Jahagirdar, A.A.; et al. NiO bio-composite materials: Photocatalytic, electrochemical and supercapacitor applications.
Appl. Surf. Sci. Adv. 2021, 3, 100049. [CrossRef]
6. Abel, S.; Jule, L.T.; Belay, F.; Shanmugam, R.; Dwarampudi, L.P.; Nagaprasad, N.; Krishnaraj, R. Application of Titanium Dioxide
Nanoparticles Synthesized by Sol-Gel Methods in Wastewater Treatment. J. Nanomater. 2021, 2021, 3039761. [CrossRef]
7. Rafatullah, M.; Sulaiman, O.; Hashim, R.; Ahmad, A. Adsorption of methylene blue on low-cost adsorbents: A review. J. Hazard.
Mater. 2010, 177, 70–80. [CrossRef]
8. Derakhshan, Z.; Baghapour, M.A.; Ranjbar, M.; Faramarzian, M. Adsorption of Methylene Blue Dye from Aqueous Solutions by
Modified Pumice Stone: Kinetics and Equilibrium Studies. Health Scope 2013, 2, 136–144. [CrossRef]
9. Dutta, K.; Mukhopadhyay, S.; Bhattacharjee, S.; Chaudhuri, B. Chemical oxidation of methylene blue using a Fenton-like re-action.
J. Hazard. Mater. 2001, 84, 57–71. [CrossRef]
10. Habib, N.R.; Taddesse, A.M.; Temesgen, A. Synthesis, characterization and photocatalytic activity of Mn2 O3 /Al2 O3 /Fe2 O3
nanocomposite for degradation of malachite green. Bull. Chem. Soc. Ethiop. 2018, 32, 101–109. [CrossRef]
11. Ochiai, T.; Fujishima, A. Photoelectrochemical properties of TiO2 photocatalyst and its applications for environmental purifi-cation.
J. Photochem. Photobiol. C Photochem. Rev. 2012, 13, 247–262. [CrossRef]
12. Wang, Y.F.; Tao, J.J.; Wang, X.Z.; Wang, Z.; Zhang, M.; Gang, H.; Sun, Z.Q. A unique Cu2 O/TiO2 nanocomposite with enhanced
photocatalytic performance under visible light irradiation. Ceram. Int. 2017, 43, 4866–4872. [CrossRef]
13. Chen, C.; Ma, W.; Zhao, J. Semiconductor-mediated photodegradation of pollutants under visible-light irradiation. Chem. Soc. Rev.
2010, 39, 4206–4219. [CrossRef]
14. Pan, C.; Zhu, Y. New Type of BiPO4 Oxy-Acid Salt Photocatalyst with High Photocatalytic Activity on Degradation of Dye.
Environ. Sci. Technol. 2010, 44, 5570–5574. [CrossRef]
Crystals 2021, 11, 1456 15 of 16

15. Ohno, T.; Sarukawa, K.; Matsumura, M. Crystal faces of rutile and anatase TiO2 particles and their roles in photocatalytic reactions.
New J. Chem. 2002, 26, 1167–1170. [CrossRef]
16. Zhang, L.; Wang, W.; Sun, S.; Jiang, D.; Gao, E. Selective transport of electron and hole among {0 0 1} and {1 1 0} facets of BiOCl
for pure water splitting. Appl. Catal. B Environ. 2015, 162, 470–474. [CrossRef]
17. Kaur, J.; Singh, J.; Rawat, M. An efficient and blistering reduction of 4-nitrophenol by green synthesized silver nanoparticles.
SN Appl. Sci. 2019, 1, 1060. [CrossRef]
18. Verdine, J.C. Metal oxides in heterogeneous oxidation catalysis: State of the art and challenges for a more sustainable world.
ChemSusChem 2019, 12, 577–588.
19. Alam, M.W. Electrochemical Sensing of Dextrose and Photocatalytic Activities by Nickel Ferrite Nanoparticles Synthesized by
Probe Sonication Method. Curr. Nanosci. 2021, 17. [CrossRef]
20. Khan, M.S.; Ashiq, M.N.; Ehsan, M.F.; He, T.; Ijaz, S. Controlled synthesis of cobalt telluride superstructures for the visible light
photo-conversion of carbon dioxide into methane. Appl. Catal. A Gen. 2014, 487, 202–209. [CrossRef]
21. Alam, M.W.; Rao, T.N.; Prashanthi, Y.; Sridhar, V.; Alshoaibi, A.; Souayeh, B.; Abuhimd, H.; Ahmed, F. Application of Silica
Nanoparticles in the Determination of Herbicides in Environmental Water Samples Using Liquid Chromatography-Mass
Spectroscopy. Curr. Nanosci. 2020, 16, 748–756. [CrossRef]
22. Fujishima, A.; Hashimoto, K.; Watanabe, T. TiO2 Photocatalysis Fundamentals and Applications, A Revolution in Cleaning; BKC: Tokyo,
Japan, 1999.
23. Fujishima, A.; Honda, K. Photolysis-decomposition of water at the surface of an irradiated semiconductor. Nature 1972, 238, 37–38.
[CrossRef]
24. Muthee, D.K.; Dejene, B.F. Effect of annealing temperature on structural, optical and photocatalytic properties of titanium dioxide
nanoparticles. Heliyon 2021, 7, e07269. [CrossRef] [PubMed]
25. Chaturvedi, S.; Dave, P.N.; Shah, N. Applications of nano-catalyst in new era. J. Saudi Chem. Soc. 2012, 16, 307–325. [CrossRef]
26. Ziental, D.; Czarczynska-Goslinska, B.; Mlynarczyk, D.T.; Glowacka-Sobotta, A.; Stanisz, B.; Goslinski, T.; Sobotta, L. Titanium
dioxide nanoparticles: Prspects and applications in medicine. Nanomaterials 2020, 10, 387. [CrossRef] [PubMed]
27. Mahshid, S.; Askari, M.; Ghamsari, M.S. Synthesis of TiO2 nanoparticles by hydrolysis and peptization of titanium iso-propoxide
solution. J. Mater. Process. Technol. 2007, 189, 296–300. [CrossRef]
28. O’regan, B.; Gratzel, M. A low cost, high efficiency solar cell based on dye sensitized colloidal TiO2 films. Nature 1991, 353, 737–740.
[CrossRef]
29. Eidsvåg, H.; Bentouba, S.; Vajeeston, P.; Yohi, S.; Velauthapillai, D. TiO2 as a Photocatalyst for Water Splitting—An Experimental
and Theoretical Review. Molecules 2021, 26, 1687. [CrossRef]
30. Li, G.; Richter, C.P.; Milot, R.L.; Cai, L.; Schmuttenmaer, C.A.; Crabtree, R.H.; Brudvig, G.W.; Batista, V.S. Synergistic effect
between anatase and rutile TiO2 nanoparticles in dye-sensitized solar cells. Dalton Trans. 2009, 10078–10085. [CrossRef]
31. Ahn, W.-Y.; Sheeley, S.A.; Rajh, T.; Cropek, D.M. Photocatalytic reduction of 4-nitrophenol with arginine-modified titanium
dioxide nanoparticles. Appl. Catal. B Environ. 2007, 74, 103–110. [CrossRef]
32. Ni, M.; Leung, M.K.; Leung, D.Y.C.; Sumathy, K. A review and recent development in photocatalytic water-splitting using TiO2
for hydrogen pro-duction. Renew. Sustain. Energy Rev. 2007, 11, 401–425. [CrossRef]
33. Han, F.; Kambala, V.S.R.; Srinivasan, M.; Rajarathnam, D.; Naidu, R. Tailored titanium dioxide photocatalysts for the degradation
of organic dyes in wastewater treatment: A review. Appl. Catal. A Gen. 2009, 359, 25–40. [CrossRef]
34. Liu, Z.; Wang, R.; Kan, F.; Jiang, F. Synthesis and Characterization of TiO2 Nanoparticles. Asian J. Chem. 2014, 26, 655–659.
[CrossRef]
35. Dubey, R.S.; Krishnamurthy, K.V.; Singh, S. Experimental studies of TiO2 nanoparticles synthesized by sol-gel and sol-vothermal
routes for DSSCs application. Results Phys. 2019, 14, 102390. [CrossRef]
36. Devi, R.; Venckatesh, R.; Sivaraj, R. Synthesis of Titanium Dioxide Nanoparticles by Sol-Gel Technique. Int. J. Innov. Res. Sci. Eng.
Technol. 2014, 3, 15206–15211. [CrossRef]
37. Chu, L.; Qin, Z.; Yang, J.; Li, X. Anatase TiO2 nanoparticles with exposed (001) facets for efficient dye-sensitized solar cells.
Sci. Rep. 2015, 5, 12143–12152. [CrossRef]
38. Jule, L.T.; Ramaswamy, K.; Bekele, B.; Saka, A.; Nagaprasad, N. Experimental investigation on the impacts of annealing temperatures
on titanium dioxide nanoparticles structure, size and optical properties synthesized through sol-gel methods. Mater. Today Proc. 2021,
45, 5752–5758. [CrossRef]
39. Babji, P.; Rao, I.N. Catalytic reduction of 4-nitrophenol by using Fe3+ and Ag+ Co-doped TiO2 nanoparticles. Int. J. Sci. Res. 2015,
4, 2636–2641.
40. Vijayalaxmi, R.; Rajendran, V. Synthesis and characterization of nano TiO2 via different methods. Arch. Appl. Sci. Res. 2012, 4, 1183–1190.
41. Soler-Illia, G.; Louis, A.; Sanchez, C. Synthesis and characterization of mesostructured titania-based materials through evap-
oration induced self assembly. Chem. Mater. 2002, 14, 750–759. [CrossRef]
42. Yu, J.C.; Zhang, L.; Zheng, A.Z.; Zhao, J. Synthesis and Characterization of Phosphated Mesoporous Titanium Dioxide with High
Photocatalytic Activity. Chem. Mater. 2003, 15, 2280–2286. [CrossRef]
43. Kim, S.; Gupta, N.K.; Bae, J.; Kim, K.S. Fabrication of Coral–like Mn2 O3 /Fe2 O3 nanocomposite for room temperature removal of
hydrogen sulfide. J. Environ. Chem. Eng. 2021, 9, 105216. [CrossRef]
Crystals 2021, 11, 1456 16 of 16

44. Bagheri, S.; Shameli, K.; Hamid, S.B.A. Synthesis and characterization of anatase titanium dioxide nanoparticles using egg white
solution via sol-gel method. J. Chem. 2013, 2013, 848205. [CrossRef]
45. Jafri, N.M.; Jaafar, J.; Alias, N.; Samitsu, S.; Aziz, F.; Salleh, W.W.; Yusop, M.M.; Othman, M.; Rahman, M.; Ismail, A.; et al.
Synthesis and Characterization of Titanium Dioxide Hollow Nanofiber for Photocatalytic Degradation of Methylene Blue Dye.
Membranes 2021, 11, 581. [CrossRef]
46. Balcha, A.; Yadav, O.P.; Dey, T. Photocatalytic degradation of methylene blue dye by zinc oxide nanoparticles obtained from
precipitation and sol-gel methods. Environ. Sci. Pollut. Res. 2016, 23, 25485–25493. [CrossRef] [PubMed]
47. Kundu, A.; Mondal, A. Photodegradation of methylene blue under direct sunbeams by synthesized anatase titania nanopar-ticles.
SN Appl. Sci. 2019, 1, 280. [CrossRef]
48. Muthee, D.; Dejene, B. The effect of tetra isopropyl orthotitanate (TIP) concentration on structural, and luminescence properties
of titanium dioxide nanoparticles prepared by sol-gel method. Mater. Sci. Semicond. Process. 2019, 106, 104783. [CrossRef]
49. Gupta, N.K.; Ghaffari, Y.; Bae, J.; Kim, K.S. Synthesis of coral-like α-Fe2 O3 nanoparticles for dye degradation at neutral pH. J. Mol.
Liq. 2020, 301, 112473. [CrossRef]
50. Ghaffari, Y.; Gupta, N.K.; Bae, J.; Kim, K.S. One-step fabrication of Fe2 O3 /Mn2 O3 nanocomposite for rapid photodegradation of
organic dyes at neutral pH. J. Mol. Liq. 2020, 315, 113691. [CrossRef]
51. Gupta, N.K.; Ghaffari, Y.; Kim, S.; Bae, J.; Kim, K.S.; Saifuddin, M. Photocatalytic degradation of organic pollutants over MFe2 O4
(M = Co, Ni, Cu, Zn) nanoparticles at neutral pH. Sci. Rep. 2020, 10, 4942. [CrossRef]
52. Dagher, S.; Soliman, A.; Ziout, A.; Tit, N.; Hilal–Alnaqbi, A.; Khashan, S.A.; Alnaimat, F.; Qudeiri, J.E.A. Photocatalytic removal
of methylene blue using titania–and silica-coated magnetic nanoparticles. Mater. Res. Express 2018, 5, 065518. [CrossRef]
53. Sarigul, G.; Chamorro-Mena, I.; Linares, N.; Garcia-Martinez, J.; Serrano, E. Hybrid amino acid–TiO2 materials with tuneable
crystalline structure and morphology for photocatalytic applications. Adv. Sustain. Syst. 2021, 5, 2100076. [CrossRef]
54. Devi, S.M.; Nivetha, A.; Prabha, I. Role of citric acid/glycine-reinforced nanometal oxide for the enhancement of physio-chemical
specifications in catalytic properties. J. Supercond. Nov. Magn. 2020, 33, 3893–3901. [CrossRef]
55. Sanchez, U.A.; Chen, L.; Wang, J.A.; Norena, L.E.; Azomoza, M.; Solis, S.; Zhou, X.; Song, Y.; Liu, J. One-pot synthesis of
W-TiO2 /SiO2 catalysts for the photodegradation of p-Nitrophenol. Int. J. Photoenergy 2019, 2019, 13. [CrossRef]