Journal of Materials Science Research and Reviews

Volume XXX, Issue XX, Page XX-XX, 20YY; Article no.JMSRR.126730

Improving the Photo-catalytic

Efficiency of TiO2 by Incorporation of
Cobalt for Removal of Micropollutants
from Wastewater
Muhammad Irfan a*, Munazza Noor b, Sonia Abbas b,
Iqra Gohar b, Ahtasham Raza c and Noor Ahmad d++
a
Department of Physics, University of Okara, 3600 Punjab, Pakistan.
b Department of Physics, GGDC N0 2 DIK, 29111, Pakistan.
c Integrated Environment Laboratory, Lahore, Pakistan.
d Environmental Protection Agency-Punjab EP&CCD, Government of the Punjab, Pakistan.

Authors’ contributions

This work was carried out in collaboration among all authors. Author MI writing and analyzing original
manuscript. Authors MN, SA, IG and HE Each author contribute in the experimental design and
writing the manuscript. Author RPP carrying out measurements. All authors read and approved the
final manuscript.

Article Information
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This journal follows the Advanced Open Peer Review policy. Identity of the Reviewers, Editor(s) and additional Reviewers,
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Received: DD/MM/20YY
Original Research Article Accepted: DD/MM/20YY
Published: DD/MM/20YY

ABSTRACT

The research focuses on the fabrication and use of Co-doped titanium dioxide (TiO₂) nanocrystals
for efficient industrial wastewater treatment, specifically improving photocatalytic destruction of
methylene blue (MB). The crystal structure, including phase identification, crystalline size, texture,
_____________________________________________________________________________________________________
++
Deputy Director;
*Corresponding author: Email: [email protected];

Cite as:
 Irfan et al.; J. Mater. Sci. Res. Rev., vol. xx, no. xx, pp. xx-xx, 20YY; Article no.JMSRR.126730

stress, and strain, has been verified by X-ray powder diffraction (XRD). The average crystallite size
of nanocrystals decreased from 65.69 nm to 32.62 nm with the incorporation of 9% Co into the
TiO2 crystal lattice. The presence of Ti-O and C=O functional groups in the FTIR spectra shows the
successful doping of Co. The optical band gap reduced from 3.39 eV for undoped TiO 2 to 3.06 eV
for 9 % Co-doped TiO2, as confirmed by UV-Vis spectroscopy. The photocatalytic activity of the
samples was studied utilizing the degradation of methylene blue as a model substance. Which was
substantially increased from 5.86% for pure TiO 2 to 23.01% for Co-0.9%, with a rate constant of
2.17 x 10-3 min-1. This study shows that Co-doped TiO₂ is a viable substance for wastewater
management, and offers an efficient and sustainable technique for degrading MB under ambient
circumstances.

Keywords: Co-doped TiO2 nanocrystals; single step sol-gel method; photo-degradation; methylene
blue dye; wastewater.

1. INTRODUCTION trioxide (WO3) [24] are a few metal oxide

semiconductor (MOS) materials that have shown
Metal oxide semiconductors, advanced functional great promise as photocatalysts [28,29,24].
materials such as two-component (alloyed), and Among all of these MOS TiO2 has attained great
metal-oxide nanoparticles have a significant significance in AOPs due to its remarkable
impact on a range of applications in science and features, including chemical and physical
technology [1,2,3,4,5]. In recent decades, air and stability, non-toxicity, strong oxidative power, low
water pollution in urban areas produced mainly cost, antibacterial activity, environmental
by automobiles and the chemical industry has friendliness, highly solar-activated surface, etc
become a serious threat to public health [6,7]. [30,31,32,33]. TiO2 exists in three phases,
However, toxic organic compounds like anatase, rutile, and brookite, of which anatase
pesticides, dyes, phenols, and the associated and rutile are known to be potentially active
environmental hazardous pollutants are materials for many applications; such as in
discharged into the aquatic environment through photocatalysis, water purification, solar cells,
various anthropogenic inputs [8,2,9,10,11,12]. sensors, paints, etc. But the main drawback of
Despite their low concentration, the presence of these systems, for many of these applications, is
these contaminants is still a major concern over their absorption in the UV region, which
public health and a major obstacle to water corresponds to only 3–5% of solar radiation
recycling due to their bio-recalcitrant and acute [34,35,9]. However, the practical application of
toxicity [13,14,15]. The method of “advanced TiO2 is limited by two main factors. Firstly, only a
oxidation processes” (AOPs) appears to become small portion of the solar spectrum is absorbed in
the focus of intense interest when the process the ultraviolet UV light region due to the wide
can be driven by solar, UV, or visible light. band gap nature of titania (3.2 eV) for anatase
Among AOPs, TiO2 is generally considered to be and (3.0 eV of rutile), secondly, the
one of the important evergreen photocatalysts recombination rate of photogenerated electron-
due to its desirable physical and chemical hole pairs is too high to be used for organic
properties against photochemical corrosion, pollutant degradation in practice. Therefore TiO2
efficient photocatalytic activity, high needs to attain photocatalytic response in a
photostability, low cost, and toxicity [16,17,18,9]. border range extending into visible light. To solve
Photocatalysis involves activating a catalyst these difficulties, numerous researchers worked
material with light energy to speed up chemical on titanium dioxide semiconductors utilizing
reactions. When a photocatalyst is exposed to different approaches to improve the
light energy, the photons excite electrons in the photocatalytic performance of TiO2 [36]. Toubal
valence band (VB) to the conduction band (CB), et al. (2017) produced Co-doped TiO2
resulting in electron-hole pairs. The holes left nanoparticles via sol-gel synthesis and measured
over in the VB can react with adsorbed species their electrical characteristics, finding that Co-
like water or organic compounds, whereas, the doping significantly increased TiO2 conductivity
excited electrons in the CB have a greater [27]. Chanda et al (2021) used the sol-gel spin
energy and can participate in different redox coating approach to create Co-doped TiO2 thin
processes [19,20,12,21]. Titanium dioxide (TiO2) films, resulting in high refractive index TiO 2 nano-
[22], zinc oxide (ZnO) [23], SnO2 [24], Fe2O3 [25], films due to the integration of Co as a dopants
CuO [26], Co-doped TiO2 [27], and tungsten material in the TiO2 lattice. Cobalt was chosen as

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a dopant material because, when exposed to UV doping, and this led to a much greater
light, Co-TiO2 forms electron-hole pairs, which photocatalytic activity for organic pollutant
may subsequently combine with water molecules degradation. The relationship between the
and oxygen in the air to create highly reactive morphology, structure, optical properties, and
oxygen species such as hydroxyl radicals (OH•) photocatalytic activities of Co-doped TiO2
[37,38,39]. These radicals are powerful oxidants nanocrystals was investigated in detail [36].
capable of breaking down organic pollutants and
eliminating the microbiological contaminants 2. MATERIALS AND METHODS
found in wastewater. Currently, the most frequent
preparation techniques include the gas phase Experimental details: All precursor ingredients,
process, hydrothermal method, sol-gel method, including titanium butoxide IV, cobalt sulfate, and
solvothermal method, and detonation method. aqueous HCl, were obtained from Sigma Aldrich
Among the several synthesis processes the most (Germany), and ANALAR was used to prepare
prevalent is Solgel for material preparation. Sol- the undoped and Co-doped TiO2 nanoparticles
gel is one of the most utilized techniques; that is utilizing a single-step sol-gel process. No further
used mostly for creating thin films and nano purification of the precursor materials was
powder photocatalysts. Many studies revealed carried out; utilized as it is obtained from the
that Solgel is a very simple technique, low seller.
temperature operatable, yielding a large number
of products, producing homogeneous materials Preparation of Un-doped TiO2: The precursor
with small crystallite size and greater surface Substance 10 mL of titanium butoxide (TBO) was
area which is the essential property for added to with 20 mL of distilled water. After 20
nanomaterials [40,20,41,42,43,44]. minutes of constantly stirring at ambient
temperature (27 0C), 5 mL concentrated HCl was
In the present work, we have prepared and added dropwise to the solution, and steering was
characterized pure TiO2 and cobalt-doped TiO2 discontinued after 40 minutes. To make xerogel,
with 7% and 9% doping. The reduced crystallite the warmed samples were dried in an oven at
size of the Co-doped TiO2 nanocrystals can 150 0C for 12 hours. Bulk crystals then formed,
change the shape of TiO2, resulting in a higher indicating that the gel had entirely dried. The
surface-to-volume ratio and a greater number of dried gel is crushed and pestled into fine powder.
active sites. Therefore, the photodegradation of Calcination at 500 0C for 4 hours was
methylene blue designated that the separation performed to eliminate any probable
efficiency of the photogenerated electron and contaminants that degrade at high temperatures
hole pairs was mainly improved due to Co- from the sample.

Fig. 1. Schematic diagram of Single Step Sol-gel Synthesis of Co-doped TiO2

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Preparation of Co-doped TiO2 nanocrystals: Co ions can reduce the energy barrier for this
Titanium butoxide (TBO) 10 mL was added to phase transition, resulting in the creation of an
(0.7 g) Co(SO4), and after 20 minutes of extra peak of the rutile phase. Scherrer equation
constantly stirring at room temperature (27 0C), (1) was used to determine the average crystallite
20 mL filtered water and several drops of HCl size of all the samples.
were progressively put into the solution, and
steering was stopped after 40 minutes. Warm Dave = (0.94)λ / βcosθ (1)
samples were dried for 12 hours in a hot oven at
150 0C to produce xerogel. Due to the elimination Here θ is the diffraction angles, D is the average
of water, the dispersed gel shrank and became a crystal size, λ is the corresponding incident
viscous paste. Bulk crystals then formed, wavelength of the diffraction X-ray exposure
indicating that the gel was entirely dried. The (1.5418 A0), and β is the full-width half maximum
dried gel was then ground into a fine powder with (FWHM) of the diffracted peaks. The average
a mortar and pestle. To remove any suspicious crystallite sizes (D) for pure and Co-doped (7%
impurities, Co-doped TiO2 was calcined at 500 and 9%) TiO2 nano-crystals were estimated as
0C for 4 hours. 34.52 nm, 32.62 nm, and 65.69 nm employing
equation (1), which is also presented in Table 1.
Photodegradation Activity of all prepared The inclusion of Co+2 ions into the TiO2 lattice
samples: The resulting nanocrystals were then resulted in a consistent drop in the
exposed to direct sunshine, and the crystallite size of the TiO2 nanocrystals. Several
photodegradation rate using methylene blue other essential crystal characteristics, including
(MB) at an initial dye amount of 10 mg per 500 microstrain, dislocation density, and crystallinity,
ml was calculated for 1 mg of catalysts per 100 have been measured and illustrated in Table 1
ml of dye mixture. To assess the samples' [46].
photocatalytic capability, the UV-vis
absorption spectra were examined by exposing FTIR Analysis: Fourier Transform Infrared
them to different periods of visible light. The (FTIR) Spectra are commonly employed to
available sunshine exposure period explore the structure or functional group of a
ranged from 0 to 120 minutes, with 15-minute multi-component system [46]. In FTIR, the
intervals. intensity of IR radiation correlates to the energy
gaps across quantized vibrating modes. When
3. RESULTS AND DISCUSSION the infrared ray meets the energy requisite for a
molecular transition, the molecule absorbs it,
XRD analysis: Fig. 2 shows the XRD spectra of causing the associated vibrating mode to be
all the synthesized samples. The highly intense stimulated. Each absorbing wavelength can be
and sharp peak round of about 250 observed in observed as a peak in the FTIR spectrum. These
all samples confirms the highly crystalline peaks' positions correlate to the vibrational
anatase phase of TiO2 nanocrystal. The sharp frequencies of distinct bonds, making it possible
crystalline peaks were observed at 2 theta to identify particular functional groups. The FTIR
degrees 250, 380, 480, 550, 560, and 630 spectra of all synthesized samples pure and
respectively with respective (hkl) reflection cobalt-doped TiO2 NC’s were observed in the
planes (101), (004), (222), (200), (105) and wave number range of (4000 - 4000) cm-1 as
(112). Furthermore, Co-doped TiO2 samples shown in Fig. 3. Ti-O-Ti bonds are responsible
reveal mixed phases of TiO2 anatase as well as for the sharp band observed in all samples about
the rutile phase. It may be due to the 421 cm−1. The broadband is caused by the dipole
incorporation of Co+2 ions can replace the Ti+4 moment of nanocrystals around 1586 cm−1
ions in the TiO2 lattice which can create crystal indicating the hydroxyl group of O-H stretching
defects owing to changes in their ionic radii and vibrations [36]. The peak at 2371 cm−1
valence states. This deformation in the TiO 2 represents the asymmetric vibration (C=O) of
crystal can alter the crystal structure, resulting in CO2 absorbed from the air during the thermal
the simultaneous existence of anatase and rutile treatment of titanium oxides [47]. The broad
phases [45]. An extra peak observed at 42.310 in bands at 1759 cm-1 and 3804 cm-1 are attributed
Co-doped TiO2 samples is due to Cobalt doping to stretching and bending vibrations of water
can change the phase stability of TiO₂, molecules (H2O) that are adsorbed at the surface
facilitating the transition from anatase to rutile. of the nanocrystals [48].

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101 Pure TiO2

0.7%
0.9%
105
004
222
Intensity (a.u)
200 002 211

20 30 40 50 60 70

2 Theta (Degree)
Fig. 2. XRD spectra of the pure and co-doped TiO2 nanocrystals

Table 1. Detailed photochemical properties of pure and Co-doped TiO2 nanocrystals

Dopants Crystallize Micro Dislocation Density Crystallinity Eg (eV)

Concentration W% sizes (nm|) strain (10-3) (nm)-2 x 10 %
TiO2- Pure 65.69 0.584 0.8303 33.522 3.39
TiO2–Co 0.7 w% 34.52 0.492 1.5909 91.164 3.27
TiO2–Co 0.9 w% 32.62 0.415 1.544 55.53 3.06
transmittance (%)

3804 2377
1750
1587

PURE TiO2
421
7%
9%

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (Cm-1)

Fig. 3. FTIR spectra of the pure and co-doped TiO2 nanocrystals

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(a) pure
1.2 0.7 %
0.9 %
absorbtion (au) 1.0

0.8

0.6

0.4

0.2

0.0
300 400 500 600 700 800

wavelenght (nm)

Pure TiO2 (b)

Co-0.7 %
Co-0.9%
-1 2
IDBandgap (eVcm )

3.39

3.06
1 2 3 3.27 4 5
Energy (eV)
Fig. 4. (a) UV visible absorbance spectra and (b) Indirect Bandgap Vs energy (eV) of the
fabricated pure, 0.7 and 0.9 % Co-doped TiO2 nanocrystals

UV analysis: Fig. 4 depicts the UV-Vis doped TiO2 (0.7% and 9%) have been observed
absorbance spectra of all the produced samples, at 366, 379, and 405 nm, correspondingly. Fig. 4
both pure and Co-doped TiO2, in the 200-800 nm demonstrates that the absorption edge shifts
region. Absorption peaks represent transitions towards longer wavelengths region while the
between electrical energy levels. The absorption percentage of Co enhances in the TiO 2 lattice
edges of pure and different concentrations of Co- structure indicating an alternate decline in the

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optical band gap of the TiO2. The indirect pure TiO2 nanocrystals during 120 min exposure
band gap transition was estimated using to direct sunlight. The degradation of MB
Equation 2. increases significantly up to 14.76 % and 23,01
% in the presence of 0.7 and 0.9 % Co-doped
(αhυ)n = A(hυ – Eg) (2) TiO2 nanocrystals. Enhancing photodegradation
of MB in the presence of Co-doped TiO2
In the above equation, α is the absorption nanocrystals owing to Photocatalyst activity is
coefficient calculated from UV data, h is the determined by two primary factors: greater
planks constant, n = 2 for the indirect allowed surface area and increased light absorption
transition and A represents the absorbance of capacity in the visible spectrum [50]. Broad
the material. The indirect optical band gap humps might suggest an appearance of
calculated values are 3.39 eV for pure TiO2, 3.27 intermediate energy states within the band gap,
eV, and 3.06 eV for pure and 7% and 9% Co- which are caused by Co+2 ions. These states,
doped TiO2 samples [39]. The declining behavior also known as "trap states" or "mid-gap states,"
in optical band gap Eg is caused by the addition facilitate more light absorption at lower energies
of Co+2 ions in TiO2, which activates the than the pure band gap, which extends
nanocrystal material in the higher wavelength absorption into the visible domain of light. The
portion of the visible spectrum of light. It may be photodegradation efficiency of all produced
due to the development of new nanocrystals was determined using the following
energy levels between the valance and equation:
conduction band of the TiO2 crystals caused by
the inclusion of Co+2 ions. Co-doped TiO₂ has a Photodegraded efficiency % = (Co - Ct / Co) ×
narrower band gap due to added 100% (3)
energy levels from dopants. These intermediate
states enable electrons to switch with less Where Co and Ct are before illumination and after
energetic photons, transforming absorption to the MB degradation concentrations, respectively
visible spectrum and increasing the [51].
material's photocatalytic effectiveness under
sunlight. To further figure out how MB dye degrades
photocatalytically, Fig. 6 (a,b) displays the
Photocatalytic activity: The produced nano- pseudo first-order model reaction kinetics of pure
crystals were then exposed to direct sunshine, and, Co-doped TiO2. The dynamics of
and the rate of photo-degradation using the first-order model are defined in Formula (4)
methylene blue (MB) at initial dye concentrations below.
of 10 mg per 500 mL was calculated for 1 mg of
catalysts per 100 mL of dye solution. To assess lnC0 / Ct = kt (4)
the samples' photocatalytic capacity, the UV-Vis
absorption spectra were examined by exposing Where C0 and Ct represent the amount of MB
them to different periods of visible light. The degraded in exposure to direct sunlight for a total
available sunshine exposure period ranged from of 120 minutes, divided into 15-minute intervals.
0 to 120 minutes, with 15-minute intervals. A The symbols t and k represent the reaction's time
series of preliminary experiments were and rate constants, respectively. A tauc plot was
conducted to determine the influence of used to analyze the linear fitting vs. irradiation
photocatalysis and adsorption on photocatalytic time of MB photocatalytic degradation, as shown
transformation. Photocatalysis studies were in Fig. 6 (b). The projected kinetic degradation
conducted at pH = 6 and a concentration of 1mg rate constant (k) can be determined by studying
Co-doped TiO2 in 100 ml of MB solution [49]. It is the gradient of the fitting curve. Under direct
observed that the methylene blue steadily sunlight, it was discovered that the estimated
degrades over time after each 15-minute interval values of (k) for pure TiO2 and (0.7 &0.9) % Co-
under continuous exposure to sunlight. Fig. 5 doped TiO2 are (0.45, 1.38, and 2.17) x 10-3 min-
1, as shown in Table 2. As shown in Fig. (6-b) the
displays the findings of the photocatalytic
decomposition of MB under visible sunlight in the rate constant for MB degradation increases with
presence of pure and Co-doped TiO2 an increase in the concentration of the Co in TiO 2
nanocrystals. Fig. (5-a) reveals very minor nanocrystals and the half-life decreases
degradation of MB (5.86%) in the presence of correspondingly [52].

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Fig. 5. UV vis absorbance (a) Pure s (b) Co-0.7 % (c) Co-0.9 % (d) Photodegradation Efficiency
Vs Exposer Time of all the fabricated samples

Fig. 6. Pseudo First-order model reaction kinetics (a) Ct/Co %, (b) ln (Ct/C0) pure, 0.7 % and 0.9
% Co-doped TiO2 nano-photocatalysts

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Table 2. Detailed photodegradation parameters of pure and Co-doped TiO2 added MB

Dopant Concentration Rate Constant k x Residual Half-life of Dye t1/2 x

w% 10-3 (min-1) Concentration (R2) 10-3(min)
Pure TiO2 0.45 0.869 1.54
0.7 % Co-TiO2 1.38 0.933 0.50
0.9 % Co-TiO2 2.17 0.965 0.32

Photo-degradation mechanism: When the MB Cobalt ions (Co+2) provide energy levels to the
solution is in the presence of band gap of TiO₂. This lowers the band gap
fabricated nanocrystals subjected to direct energy, allowing visible light to be absorbed
sunlight, Co-doped TiO₂ absorbs photons with while also improving electron-hole pair
energy equivalent to or exceeding its band gap. separation by capturing electrons or holes,
This energy stimulates electrons lowering their recombination rate.
from the valence band (VB) to the conduction Photogenerated electrons in the CB and holes in
band (CB), resulting in electron-hole pairs (e-, the VB undergo redox interactions with water
h+). Photogenerated electrons migrate to the (H₂O) and oxygen (O₂) molecules adsorbed on
outermost layer of TiO2 nanocrystals and the TiO₂ surface. These processes produce
transform molecular oxygen (O2) reactive oxygen species (ROS), such as hydroxyl
into reactive superoxide (O2−). After holes radicals (•OH) and superoxide anions (O2-).
created by sunlight approach the surface, they
can oxidize hydroxide ions (OH-) or water (H2O), 9 % Co-doped TiO2 + hv → e- (CB) + h+ (VB)
producing hydroxyl radicals (•OH). Methylene
blue molecules get destroyed by hydroxyl e− + O2 → O2−
radicals (•OH) and superoxide radicals (O 2−),
causing the complicated chemical h+ + H2O → •OH + H+
arrangement of MB to disintegrate into smaller,
harmless, or environment-friendly substances •OH / •O-2 + MB → Intermediates (starts
like CO2, H2O, and other least hazardous decolorization)
inorganic elements.
Intermediates + •OH / •O-2 → CO2 + H2O + less
TiO2 + hν → e− + h+ (5) destructive ions

Fig. 7. Schematic diagram of the photo-degradation of MB in the presence of Co-doped TiO2

nanocrystals

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Table 3. Comparison of current research with previous similar studies

Commercial Photocatalyst Quantity Degration % Exposer Reference

Dye Time (min)
RB19 ZnO-KIL 2-1 800 mg/L 22 120 [53]
MB Cu-TiO2 5 mg/L 17 120 [54]
MG Cd-ZnO 500 mg/L 18 120 [55]
SMX Co-Doped TiO2 1.65 mg/L 9.88 120 [56]
MB Co-TiO2 1 mg/L 23.01 120 Current study

The ROS produced in the earlier phase are due to improved light absorption, charge
highly reactive and can oxidize organic pollutants separation, ROS production, stability, and
in MB dye, reducing them to smaller, less reusability. Future research should focus on
hazardous molecules like water and carbon developing better synthesis methods to control
dioxide. the size, shape, and dispersion of Co-doped TiO2
nanocrystals, resulting in improved photocatalytic
MB + •OH / O2- → H2O + CO2 + Reduced Co+ capabilities.
ions
DISCLAIMER (ARTIFICIAL INTELLIGENCE)
Doping TiO2 with cobalt results in a
change in TiO2's electronic arrangement. It is Author(s) hereby declare that NO generative AI
useful for aiding in the appropriate separation of technologies such as Large Language Models
electron-hole pairs and shifting light (ChatGPT, COPILOT, etc.) and text-to-image
absorption to the visible range, hence boosting generators have been used during the writing or
photocatalytic activity under sunlight. The use of editing of this manuscript.
a Co-doped TiO2 catalyst for photocatalytic
degradation is extremely effective and can be DATA AVAILABILITY STATEMENT
reused multiple times without losing
effectiveness. This makes it a sustainable The datasets generated and analyzed during the
solution for treating dye-contaminated current study are available from the
water. corresponding author upon reasonable
request.
Table 3 presents a comparison of the current
study to similar efforts in the literature. The ACKNOWLEDGEMENT
current study outperforms several earlier
publications.
The authors extend their appreciation
to the Deanship of Research and Graduate
4. CONCLUSION Studies at King Khalid University,
Saudi Arabia for funding this work through the
A single-step Sol-gel synthesis technique was Large Groups Project under grant number
used to successfully produce Co-doped TiO2 R.G.P2/175/45 and also thankful to the Deanship
nanocrystals, which were then used to degrade of Graduate Studies and Scientific Research at
MB, a commercial dye widely used in the cotton University of Bisha for supporting this work
and paint industries. The synthesized through the Fast-Track Research Support
nanocrystals were characterized through Program.
various material characterization techniques
such as XRD, FTIR, and UV which confirm the
COMPETING INTERESTS
successful doping of Cobalt into TiO2
lattice with enhanced photocatalytic and optical
Authors have declared that no competing
properties. The increase in the Cobalt
interests exist.
concentration in the TiO2 crystal lattice
reveals a gradual increase in the
photodegradation of MB and also results in the REFERENCES
reduction of the band gap energies of the TiO2
nanocrystals. Overall Co-doped TiO2 has 1. Irfan M et al. Improving photocatalytic
stronger photocatalytic activity than pure TiO 2 efficiency of ZnO nanoflowers through gold

10
 Irfan et al.; J. Mater. Sci. Res. Rev., vol. xx, no. xx, pp. xx-xx, 20YY; Article no.JMSRR.126730

incorporation for Rhodamine B pollution abatement. RSC Adv. 2022;

photodegradation. Opt Mater (Amst). 2024, 12(29):18794-805.
Aug;154:115681. DOI: 10.1039/d2ra02847f.
DOI: 10.1016/j.optmat.2024.115681. 11. Mohammed R, Ali MEM, Gomaa E,
2. Chavali MS, Nikolova MP. Metal oxide Mohsen M. Green ZnO nanorod
nanoparticles and their applications in material for dye degradation and
nanotechnology. SN Appl Sci. 2019, Jun detoxification of pharmaceutical wastes in
1;1(6):592-3. water. J Environ Chem Eng. 2020;8(5):
DOI: 10.1007/s42452-019-0592-3. 104295.
3. Maragatha J, Rajendran S, Endo T, DOI: 10.1016/j.jece.2020.104295.
Karuppuchamy S. Microwave synthesis of 12. Verma N, et al. Characterization of
metal doped TiO2 for photocatalytic Fabricated Gold-Doped ZnO Nanospheres
applications. J Mater Sci Mater Electron. and Their Use as a Photocatalyst in the
2017, Apr;28(7):5281-7. Degradation of DR-31 Dye. J Nanomater.
DOI: 10.1007/s10854-016-6185-7. 2022;2022:7532332.
4. Deng Y. Sensing mechanism and DOI: 10.1155/2022/7532332.
evaluation criteria of semiconducting metal 13. Irfan M, Khan MI, Al Huwayz M, Alwadai N.
oxides gas sensors. In: Semiconducting Synthesis, characterization, and
Metal Oxides for Gas Sensing. Singapore: photodegradation assessment of Ni and
Springer. 2019;23-51. DOI: 10.1007/978- Cd-doped TiO2 nanocrystals via sol-gel
981-13-5853-1_2. method for methylene blue under sunlight.
5. Krishna KG, Parne S, Pothukanuri N, Dig J Nanomater Biostruct. 2024;19(2):
Kathirvelu V, Gandi S, Joshi D. 953-66.
Nanostructured metal oxide DOI: 10.15251/DJNB.2024.192.953.
semiconductor-based gas sensors: A 14. Jo WK, Kim YG, Tonda S. Hierarchical
comprehensive review. Sensors Actuators flower-like NiAl-layered double hydroxide
A Phys. 2022, Jul;341:113578. microspheres encapsulated with black Cu-
DOI: 10.1016/j.sna.2022.113578. doped TiO2 nanoparticles: Highly
6. Aqeel M, Ikram M, Imran M, Ul-hamid A. efficient visible-light-driven composite
TiO2 Co-doped with Zr and Ag photocatalysts for environmental
shows highly suitable for treatment of remediation. J Hazard Mater. 2018 Sep;
polluted water. RSC Adv. 2020;2:42235- 357:19-29.
48. DOI: 10.1016/j.jhazmat.2018.05.038.
DOI: 10.1039/d0ra08718a. 15. Samadi A, et al. Stratum corneum
7. Zhao Y et al. Rapid proton exchange hydration in healthy adult humans
between surface bridging hydroxyls and according to the skin area, age and sex: A
adsorbed molecules on TiO2. Appl Catal B systematic review and meta-analysis. J
Environ. 2020;277:119234. Eur Acad Dermatol Venereol. 2022,
DOI: 10.1016/j.apcatb.2020.119234. Oct;36(10):1713-21.
8. Kononov A, et al. Online breath analysis DOI: 10.1111/jdv.18297.
using metal oxide semiconductor sensors 16. Yang Z, Qin L, Tian P, Zhang Y. Review of
(electronic nose) for diagnosis of N and metal co-doped TiO2 for water
lung cancer. J Breath Res. 2020;14(1):1- purification under visible light irradiation 2.
10. Principle of Photocatalytic Oxidation
DOI: 10.1088/1752-7163/ab433d. Process. IPCBEE. 2014;78:31-40.
9. Navidpour AH, Abbasi S, Li D, Mojiri A, DOI: 10.7763/IPCBEE.
Zhou JL. Investigation of advanced 17. Chen Y, Zeng D, Zhang K, Lu A, Wang L,
oxidation process in the presence of TiO2 Peng DL. Au–ZnO hybrid nanoflowers,
semiconductor as photocatalyst: Property, nanomultipods and nanopyramids: One-
principle, kinetic analysis, and pot reaction synthesis and photocatalytic
photocatalytic activity. Catalysts. 2023 properties. Nanoscale. 2014;6(2):874-
Jan;13(2):232. 81.
DOI: 10.3390/catal13020232. DOI: 10.1039/C3NR04558G.
10. Soni V, Singh AN, Singh P, Gupta A. 18. Juárez-Cortazar DE, et al. Doping of TiO2
Photocatalytic dye-degradation activity of using metal waste (Door Key) to improve
nano-crystalline Ti1−xMxO2−δ (M = Ag, its photocatalytic efficiency in the
Pd, Fe, Ni and x = 0, 0.01) for water mineralization of an emerging contaminant

11
 Irfan et al.; J. Mater. Sci. Res. Rev., vol. xx, no. xx, pp. xx-xx, 20YY; Article no.JMSRR.126730

in an aqueous environment. Water. 2022, sol-gel. J Sol-Gel Sci Technol. 2017;

Apr;14(9):1389. 82(2):478-89.
DOI: 10.3390/w14091389. DOI: 10.1007/s10971-017-4337-8.
19. Challagulla S, Tarafder K, Ganesan R, Roy 28. Hasanah AU, Gareso PL, Rauf N, Tahir D.
S. Structure sensitive photocatalytic Photocatalytic performance of zinc oxide
reduction of nitroarenes over TiO2. Sci and metal-doped zinc oxide for various
Rep. 2017, Aug;7(1):8783. organic pollutants. Chem Bio Eng Rev.
DOI: 10.1038/s41598-017-08599-2. 2023;10(5):698-710.
20. Khlyustova A, et al. Doped TiO2: The DOI:10.1002/cben.202300004.
effect of doping elements on photocatalytic 29. Gao X, Zhang T. An overview: Facet-
activity. Mater Adv. 2020;1(5):1193- dependent metal oxide semiconductor gas
1201. sensors. Sensors Actuators B Chem.
DOI: 10.1039/d0ma00171f. 2018;277:604-633.
21. Lee SF, Jimenez-Relinque E, Martinez I, DOI:10.1016/j.snb.2018.08.129.
Castellote M. Effects of mott–schottky 30. Patricia M, Vega B, Aracely MH, Luis HJ,
frequency selection and other controlling Mar G, Hinojosa-Reyes VRL. Visible light
factors on flat-band potential and band- photocatalytic activity of sol-gel Ni-doped
edge position determination of TiO2. TiO2 on p-arsanilic acid degradation. J
Catalysts. 2023, Jun;13(6):1000. Sol-Gel Sci Technol; 2018.
DOI: 10.3390/catal13061000. DOI:10.1007/s10971-018-4579-0.
22. Tomić J, Malinović N. Titanium dioxide 31. Trzeciak M, Miądlicki P, Tryba B.
photocatalyst: Present situation and future Enhanced degradation of ethylene in
approaches. AIDASCO Rev. 2023, thermo-photocatalytic process using
Jun;1(2):26-30. TiO2/nickel foam: Reaction mechanism;
DOI: 10.59783/aire.2023.27. 2023.
23. Modi S, et al. Photocatalytic degradation of DOI:10.20944/preprints202311.1352.v1.
methylene blue dye from wastewater by 32. Chambers C, Stewart SB, Su B, Jenkinson
using doped zinc oxide nanoparticles. HF, Sandy JR, Ireland AJ. Silver doped
Water. 2023, Jun;15(12):2275. titanium dioxide nanoparticles as
DOI: 10.3390/w15122275. antimicrobial additives to dental polymers.
24. Li Q, Zeng W, Li Y. Metal oxide gas Dent Mater. 2017;33(3).
sensors for detecting NO2 in industrial DOI:10.1016/j.dental.2016.11.008.
exhaust gas: Recent developments. 33. Bahadur J, Agrawal S, Parveen A, Jawad
Sensors Actuators B Chem. 2022, May A, Ashraf SSZ, Ghalib RM. Micro-
15;359:131579. structural, optical and dielectric properties
DOI: 10.1016/j.snb.2022.131579. of Ag doped TiO2 synthesized by sol–gel
25. Al-Musawi TJ, et al. Degradation of method. Mater Focus. 2015;4(2):134-
amoxicillin under a UV or visible light 141.
photocatalytic treatment process using DOI:10.1166/mat.2015.1228.
Fe2O3/bentonite/TiO2: Performance, 34. Choudhury B, Choudhury A.
kinetic, degradation pathway, energy Luminescence characteristics of cobalt
consumption, and toxicology studies. Optik doped TiO2 nanoparticles. J Lumin. 2012;
(Stuttg). 2023, Feb;272:170230. 132:178-184.
DOI: 10.1016/j.ijleo.2022.170230. DOI:10.1016/j.jlumin.2011.08.020.
26. Ullah F, Ghani U, Mohamed Saheed MS. A 35. Nigussie GY et al. Antibacterial activity of
PN-type CuO@TiO2 nanorods Ag-doped TiO2 and Ag-doped ZnO
heterojunction for efficient PEC water nanoparticles. Int J Photoenergy. 2018;
splitting: DFT model and experimental 2018:5927485.
investigation on the effect of calcination DOI:10.1155/2018/5927485.
temperature. Int J Hydrogen Energy; 2023, 36. Singaram B, Jeyaram J, Rajendran R,
Aug. Arumugam P. Visible light photocatalytic
DOI: 10.1016/j.ijhydene.2023.07.159. activity of tungsten and fluorine codoped
27. Toubal B, Bensaha R, Yakuphanoglu F. TiO2 nanoparticle for an efficient dye
The influence of copper-cobalt co-doping degradation; 2018.
on optical and electrical properties of 37. Anju KR, Thankapan R, Rajabathar JR, Al-
nanostructures TiO2 thin films prepared by Lohedan HA. Hydrothermal synthesis of
nanosized (Fe, Co, Ni)-TiO2 for enhanced

12
 Irfan et al.; J. Mater. Sci. Res. Rev., vol. xx, no. xx, pp. xx-xx, 20YY; Article no.JMSRR.126730

visible light photosensitive oxide for supercapacitor applications;

applications. Optik (Stuttg). 2018;165:408- 2019.
415. DOI:10.1016/j.electacta.2014.01.161.
DOI:10.1016/j.ijleo.2018.03.091. 48. El Mragui A, Zegaoui O, Daou I, Esteves
38. Essam Y, El-Nowihy GH. N-Co-Cd-doped da Silva JCG. Preparation,
TiO2 nanocomposite for efficient dye- characterization, and photocatalytic activity
synthesized solar cells. Ain Shams Eng J. under UV and visible light of Co, Mn, and
2023;102180. Ni mono-doped and (P,Mo) and (P,W) co-
DOI:10.1016/j.asej.2023.102180. doped TiO2 nanoparticles: A comparative
39. Mansour SA, Farha AH, Kotkata MF. Sol– study. Environ Sci Pollut Res.
gel synthesized Co-doped anatase TiO2 2021;28(20):25130-25145.
nanoparticles: Structural, optical, and DOI:10.1007/s11356-019-04754-6.
magnetic characterization. J Inorg 49. Garg A, et al. Photocatalytic degradation of
Organomet Polym Mater. 2019;29(4):1375- bisphenol-A using N, Co codoped TiO2
1382. catalyst under solar light. Sci Rep.
DOI:10.1007/s10904-019-01102-6. 2019;9(1):1-13.
40. Akpan UG, Hameed BH. Advancements in DOI:10.1038/s41598-018-38358-w.
sol–gel method of doped-TiO2 50. Pirbazari AE, Monazzam P, Kisomi BF.
photocatalysts. Appl Catal A Gen. 2010; Co/TiO2 nanoparticles: Preparation,
375:1-11. characterization, and its application for
DOI:10.1016/j.apcata.2009.12.023. photocatalytic degradation of methylene
41. Wang Y, Cheng H, Hao Y, Ma J, Li W, Cai blue. Desalin Water Treat. 2017;63:283-
S. Photoelectrochemical properties of 292.
metal-ion-doped TiO2 nanocrystalline DOI:10.5004/dwt.2017.20205.
electrodes. 51. Aqeel M, et al. TiO2Co-doped with Zr and
42. Dhanalekshmi KI, Magesan P, Umapathy Ag shows highly efficient visible light
MJ, Zhang X, Srinivasan N, Jayamoorthy photocatalytic behavior suitable for
K. Enhanced photocatalytic and treatment of polluted water. RSC Adv.
photodynamic activity of chitosan and 2020;10(69):42235-42248.
garlic loaded CdO–TiO2 hybrid DOI:10.1039/d0ra08718a.
bionanomaterials. Sci Rep. 2021;11(1): 52. Bahrami S, Ahmadpour A, Rohani Bastami
20790. T, Ayati A, Mirzaei S. Comparative study of
DOI:10.1038/s41598-021-00242-5. metal nanoparticles anchored TiO2 using
43. Ranjitha A, Muthukumarasamy N, polyoxometalate intermediate in
Thambidurai M, Velauthapillai D. photodegradation of azo dye pollutant in
Enhanced photovoltaic performance of aquatic environments. Inorg Chem
quantum dot sensitized solar cells with Ag- Commun. 2024;160:111986.
doped TiO2 nanocrystalline thin films. J DOI:10.1016/J.INOCHE.2023.111986.
Mater Sci Mater Electron. 53. Maučec D, Šuligoj A, Ristić A, Dražić G,
2014;25(6):2724-2729. Pintar A, Tušar NN. Titania versus zinc
DOI:10.1007/s10854-014-1935-x. oxide nanoparticles on mesoporous silica
44. Kunnamareddy M, Rajendran R, supports as photocatalysts for removal of
Sivagnanam M, Rajendran R, dyes from wastewater at neutral pH. Catal
Diravidamani B. Nickel and sulfur codoped Today. 2018;310:32-41.
TiO2 nanoparticles for efficient visible light DOI:10.1016/j.cattod.2017.05.061.
photocatalytic activity. J Inorg 54. Lee KH, et al. The comparison of metal
Organomet Polym Mater. 2021;31(6):2615- doped TiO2 photocatalytic active fabrics
2626. under sunlight for wastewater treatment
DOI:10.1007/s10904-021-01914-5. applications. Catalysts. 2023;13(9):1293.
45. Douven S, et al. Cost-effective visible LED DOI:10.3390/catal13091293.
light: From powders to films. 55. Phuruangrat A, Mad-Ahin S, Yayapao O,
46. Kiani MN, et al. Synthesis and Thongtem S, Thongtem T. Photocatalytic
characterization of cobalt-doped ferrites for degradation of organic dyes by UV light,
biomedical applications. 2023;2-8. catalyzed by nanostructured Cd-doped
DOI:10.1021/acsomega.2c05226. ZnO synthesized by a sonochemical
47. Naveen N. Investigation on physiochemical method. Res Chem Intermed.
properties of Mn substituted spinel cobalt 2015;41(12):9757-9772.

13
 Irfan et al.; J. Mater. Sci. Res. Rev., vol. xx, no. xx, pp. xx-xx, 20YY; Article no.JMSRR.126730

DOI:10.1007/s11164-015-1963-z. sulfamethoxazole drug using F-Pd co-

56. Jahdi M, Mishra SB, Nxumalo EN, doped TiO2 nanocomposites. Appl Catal B
Mhlanga SD, Mishra AK. Smart pathways Environ. 2020;267(October 2019):118716.
for the photocatalytic degradation of DOI:10.1016/j.apcatb.2020.118716.

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