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Bulletin of Chemical Reaction Engineering & Catalysis, 19 (3) 2024, 408-417

Research Article

Improving Photocatalytic Efficiency with Titanium Dioxide

Quantum Dots
Nam Duy Dao1, Tho Thi Lam2, Anh Dieu Van1, Ha Thi Thu Vu2, Hai Trung Huynh3,*

1School of Chemistry and Life Science, Hanoi University of Science and Technology, 1 Dai Co Viet Road,
Hai Ba Trung, Hanoi, Vietnam.
2National Key Laboratory for Petrochemical and Refinery Technology, 2 Pham Ngu Lao Street, Hoan Kiem District,

Hanoi, Vietnam.
3School of Materials Science and Engineering, Hanoi University of Science and Technology, 1 Dai Co Viet Road,

Hai Ba Trung, Hanoi, Vietnam.

Received: 26th June 2024; Revised: 3rd August 2024; Accepted: 4th August 2024
Available online: 25th August 2024; Published regularly: October 2024

Abstract
Titanium dioxide quantum dots (TiO2-QDs), synthesized using a microwave-assisted method, represent a significant
advancement in photocatalysis, particularly in the treatment of environmental pollutants. This study focuses on TiO2-
QDs synthesized at 200°C for a duration of 5 minutes, using titanium butoxide as a precursor. Characterization through
TEM, XRD, PL, and UV-Vis-DRS analyses revealed uniform quantum dots with an average size of 5.28 nm, a bandgap
energy of 3.22 eV, and a crystalline anatase phase, indicative of high photocatalytic activity. Notably, these TiO 2-QDs
demonstrated exceptional performance in degrading methylene blue (MB) in water, achieving a remarkable treatment
efficiency of 97.6% in 120 min, significantly outperforming both conventional titanium dioxide nanoparticles and
commercial titanium dioxide materials. The reaction conditions were evaluated based on factors such as catalyst dose,
initial MB concentration, and pH. The results indicate that optimal degradation efficiency of MB was achieved at a pH
of 7, with a catalyst dose of 0.15 g/L and at a low MB concentration. The efficiency slightly decreased to 94.5% after
five reuse cycles, emphasizing its significant reusability and stability.

Copyright © 2024 by Authors, Published by BCREC Publishing Group. This is an open access article under the CC
BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Keywords: TiO2 quantum dot; TiO2 photocatalyst; methylene blue treatment; microwave-assisted method
How to Cite: N.D. Dao, T.T. Lam, A.D. Van, H.T.T. Vu, H.T. Huynh (2024). Improving Photocatalytic Efficiency with
Titanium Dioxide Quantum Dots. Bulletin of Chemical Reaction Engineering & Catalysis, 19 (3), 408-417 (doi:
10.9767/bcrec.20176)

Permalink/DOI: https://doi.org/10.9767/bcrec.20176

1. Introduction The TiO2 has been extensively researched for

Titanium dioxide (TiO2), identified as a its application in treating pollutants in water
semiconductor by researchers Fujishima and environments, demonstrating high efficiency in
Honda in 1972 [1], has been a focal point of the degradation of organic compounds such as
extensive research for its distinctive properties dyes, pharmaceuticals, and pesticides, as well as
and broad applications. Recognized for its inorganic compounds like metals and nitrates.
outstanding photocatalytic activity, chemical The drive to enhance TiO2’s photocatalytic
stability, non-toxicity, and UV light absorption efficiency is not just about improving water
capabilities [2–4], this naturally occurring treatment capabilities; it's also about advancing
titanium oxide serves as an ideal material for environmental sustainability, reducing reliance
various applications in advanced fields like on non-renewable resources [9–14].
photoptoelectronics, photodetectors, The photocatalytic efficiency of TiO2 is
photovoltaics, and photocatalysis [5–8]. significantly influenced by several factors,
including its specific surface area, crystal phase,
* Corresponding Author. crystallite size, crystallinity, and the presence of
Email: [email protected] (H.T. Huynh) dopants. Consequently, research efforts have been

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 Bulletin of Chemical Reaction Engineering & Catalysis, 19 (3), 2024, 409
dedicated to enhancing this efficiency by more stable and controllable synthesis process. Its
increasing the surface area and porosity through cost-effectiveness and high product efficiency also
the fabrication of various structures, such as make it suitable for industrial-scale [25,29]. These
nanoparticles, nanowires, nanorods, nanosheets, quantum dots underwent detailed
mesoporous spheres, nanobelts, nanotubes, and characterization to assess their size, shape,
urchin-like clusters [15]. Additionally, chemical crystallinity and essential structural properties.
modifications involving the doping with non- Furthermore, their photocatalytic performance
metals (nitrogen, F, C, S), noble metals (Ag, Au, and stability were tested in degradation of
Pt, and Pd), or other metals (Cr, Co, V, Fe, etc.) methylene blue in water, a standard organic
are explored to reduce the bandgap energy and compound in photocatalysis studies. This test
minimize electron-hole recombination [3,16–20]. aimed to evaluate not only the quantum dot
In recent years, TiO2 quantum dot materials capacity for degrading organic pollutants but also
have garnered interest as highly potential their durability in practical applications.
materials with outstanding properties that
enhance catalytic activity [21]. Quantum dots are 2. Materials and Methods
nearly quasi-zero-dimensinal nanostructures
2.1 Materials
composed of a small number of atoms, typically
ranging in size from about 2-10 nm [22–23]. These In this study, the following reagents were
sizes are smaller than or roughly equal to the employed: titanium butoxide (97%) (TBOT),
Bohr radius of an exciton in three-dimensional isopropyl alcohol (IPA) (≥99%), ethanol (EtOH)
space, and they are small enough to exhibit (≥99%), and methylene blue, all sourced from
quantum mechanical properties [21]. "Small" in Sigma-Aldrich. Titanium dioxide nanoparticles
this context is defined in relation to the (TiO2-NP, TiO2 99.9%, APS 25 nm) were acquired
characteristic size of the electron-hole pair from Degussa, while commercial titanium dioxide
(exciton) binding in semiconductor materials. As a (TiO2-CM, 99% purity) was purchased from
result, the photocatalytic properties are Xilong. An aqueous MB solution of 10 ppm was
enhanced, making better use of the stimulating used as the model reagent in the photocatalytic
photon energy and reducing electron experiments. Deionized water (DI) used in all
recombination [21,22,24]. Unlike nano sized TiO2 experiments (18 MΩ cm−1 in resistivity) was
particles, TiO2 quantum dots have small and produced in the laboratory.
uniform particle sizes, do not aggregate, exhibit
high photocatalytic activity, and maintain high 2.2 Synthesis of Titanium Dioxide Quantum Dot
stability while being reusable [25].
The synthesis of TiO2-QDs using the
Published studies have focused on sol-gel
microwave-assisted method as follows: initially,
methods using precursors, such as titanium
10 mL of IPA was slowly added to 10 mL of TBOT,
isopropoxit, titanium butoxide, and inorganic
and the mixture was continuously stirred for 15
salts like titanium tetrachloride as well as
min to obtain solution A. Next, solution A was
hydrothermal methods using precursors like
slowly added to 100 mL of deionized water (DI) in
titanium (IV) bis(ammonium lactate)dihydroxide
a 250 mL beaker, and the mixture was
(TiBALDH) and titanium oxychloride (TiOCl2), or
continuously stirred for 1 h to form solution B. The
inorganic salt Ti(SO4)2. These methods have
entire solution B was transferred to two 100 mL
yielded relatively uniform particle sizes with size
teflon containers and placed in a microwave
distributions ranging from 2.5 to 7 nm, with only
device. The reaction was carried out in a
Shim et al. achieving an average size of 15 nm [24–
microwave oven with the following settings:
32]. Most materials obtained from these studies
preheating time of 10 min from room temperature
have lower bandgap energies than that of anatase
to 200 °C, followed by a 5-min reaction at 200 °C,
materials, typically around 3.2 eV, although some
and then cooled to room temperature. The catalyst
materials have very large bandgaps, as seen in
was then recovered by centrifugation at a speed of
Rehan Danish et al., 2014 research, reaching as
5500 rpm. The catalyst was washed with EtOH at
high as 4.35 eV, which can limit the visible light
least three times to remove any residual products
absorption [25,31–32].
and then dried at 70 °C.
In this study, TiO2 quantum dots were
The resulting solid product was finely ground
synthesized using a microwave-assisted method.
and calcined in an air environment at 450 °C for 2
This method utilized a microwave oven, taking 10
h, with a heating rate of 5 °C per min. The
min to reach a temperature of 200 °C and an
material was then naturally cooled to room
additional 5 min for the synthesis of the material.
temperature to enhance the crystallization
This method offers significant benefits, including
process, achieve uniform and stable crystal sizes,
a reduced synthesis time and lower energy
and improve the photocatalytic activity. Finally,
consumption compared to both the sol-gel and
the product was ground again.
hydrothermal methods. Moreover, it features a

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 Bulletin of Chemical Reaction Engineering & Catalysis, 19 (3), 2024, 410
2.3 Characterizations reaction. The photocatalytic activity testing
apparatus was placed inside a sealed chamber,
TiO2 quantum dots were characterized for
equipped with a stirring device to ensure uniform
their crystalline phase composition and structures
mixing and enhance treatment efficiency. Inside
by X-ray diffraction (XRD) measurements using a
the system, there was also an exhaust fan to
PANalytical X'Pert PRO instrument. Surface
ensure proper air circulation within the entire
morphology and material size were assessed using
system.
a Transmission Electron Microscope (TEM)
The general experimental procedure is as
(Philips Tecnai 10 Microscope) operating at 200
follows: Prepare 0.1 g of catalyst (TiO2-QDs, TiO2
kV. Surface morphology, structure, and
NPs, TiO2 TM) and add it to 400 mL of MB
composition were analyzed using Scanning
solution with a concentration of 10 ppm. The
Electron Microscopy (SEM), and Energy
mixture is stirred in the dark condition until
Dispersive X-ray (EDX) techniques with a
adsorption/desorption equilibrium condition.
TM4000Plus tabletop Microscope (HITACHI).
Subsequently, the solution was introduced into
The UV-Vis diffused reflectance spectroscopy
the photoreactor for the extended light irradiation
(UV-Vis-DR) of the samples was measured using
experiment. According to the sampling schedule,
a JASCO V-750 spectrophotometer.
catalyst samples were centrifuged using a
Photoluminescence of the samples was recorded
centrifuge device (Centrifuge model DSC158T,
using an iHR 550 Horiba instrument. Raman
Taiwan), and the MB concentration was
spectroscopy was performed using a Renishaw in
determined through UV-Vis Spectrophotometer
Via Raman system with a 514 nm laser.
(model UV-2600, Shimadzu, Japan) at a
wavelength of 663 nm. Photocatalytic degradation
2.4 Photocatalytic Tests
was assessed based on Ct/C0 vs. time, where C0
The investigation of photocatalytic activity and Ct represent the MB concentrations in the
and material durability was conducted by solution before irradiation (t = 0) and after
comparing three samples: TiO2-QDs, TiO2 NPs irradiation for t minutes, respectively.
and commercial TiO2 CM. The selected solution The photocatalytic degradation efficiency of
for treatment was methylene blue, which is a MB was calculated as followed:
polycyclic aromatic compound commonly used as
a representative model for experiments involving C0 − Ct
the degradation of Persistent Organic Pollutants. % =  100 (1)
C0
The experiment was carried out using a high-
pressure mercury lamp OSRAM 150W as the
The reusability test incorporated a procedure
white light source, and the light intensity was
in which the catalyst material was collected after
measured using an advanced light meter from
each photocatalytic degradation experiment. Each
Geneq with the result showing the
experimental cycle included 120 min of
photoluminescence intensity of 5.0 mW.cm−2.
irradiation, following which the materials were
Methylene blue solution was placed in a double-
isolated from the mixture using filtration and
walled glass beaker, which was temperature-
centrifugation processes. To prepare them for the
controlled using a heating system to maintain a
next cycle, these materials were then dried at a
constant temperature of 25 °C throughout the
temperature of 100 °C.

(b)

Figure 1. TEM image (a) and (b) Particle size distribution of TiO 2-QDs.

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 Bulletin of Chemical Reaction Engineering & Catalysis, 19 (3), 2024, 411
3. Results and Discussion calculated bandgap energy of TiO2-QDs is 3.22 eV,
which is higher than that of TiO2 CM at 2.98 eV
3.1 Characterizations of Material
and TiO2 NPs at 2.95 eV. This higher bandgap
The surface structure of TiO2 material enhances their photocatalytic activity due to the
through TEM imaging results is presented in quantum confinement effect, which reduces
Figure 1. The Transmission electron microscopy electron-hole recombination. The increased
(TEM) image in Figure 1 illustrates the uniform bandgap allows TiO2-QDs to utilize UV light more
spherical particles in the TiO2-QDs material. The effectively, making them crucial for photocatalytic
material was synthesized using a microwave applications.
method, with particle sizes ranging from 3.1 to 10 The increase in bandgap energy of the
nm, with the main distribution occurring in the microwave sample can be explained by the Bras
range of 4-7 nm. The average value of the TiO2- model, specifically that when the TiO2 particle
QDs sample size was found to be 5.28 nm. size is less than 10 nm, the bandgap energy
The fluorescence spectrum of the TiO2-QDs is increases slightly as the particle size decreases
shown in Figure 2. Fluorescence emission was [34]. In addition, factors affecting the bandgap
observed in the range of 400-800 nm when excited energy include the crystal phase of the material,
with light at a wavelength of 360 nm. The results as well as the synthesis method and conditions
indicate that in the fluorescence spectrum of TiO2- such as temperature and atmosphere [35–36].
QDs synthesized using the microwave-assisted The crystal structure of TiO2 quantum dots
method, there is a peak maximum at (QDs) was studied using X-ray diffraction (XRD),
approximately 525 nm. Here, the peak at 525 nm as shown in Figure 4. The XRD pattern reveals
is attributed to the indirect recombination of the the presence of distinct diffraction peaks at
photogenerated electrons and holes via the oxygen 25.40°, 37.2°, 38.50°, 37.2°, 48.20°, 54.2°, 55.1°,
vacancies [33]. Additionally, indirect
recombination at the 525 nm peak is noticeable in
the TiO2-QDs sample with a fairly distinct peak.
To investigate the absorption properties and
band structure of the obtained TiO2-QDs, UV-Vis
diffuse reflectance spectroscopy (UV-Vis DRS)
was conducted alongside the TiO2 NPs sample.
The results, shown in Figure 3(a), reveal that the
absorption edge of the microwave-synthesized
sample has a narrower bandgap compared to the
TiO2 NPs sample. UV-Vis DRS spectral analysis
not only provides information about the
absorption regions of the catalyst materials but
also allows for the calculation of the bandgap
energy (Eg). The bandgap energy was calculated
using the Tauc plot of (Ahυ)1/2 versus wavelength
hυ. The results are presented in Figure 3(b). The

Figure 2. Photoluminescence (PL) spectra of TiO2- Figure 3. UV-Vis (a) and bandgap (b) of TiO2-QDs
QDs. and TiO2 NPs.

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 Bulletin of Chemical Reaction Engineering & Catalysis, 19 (3), 2024, 412
62.8°, 68.9°, 70.4°, and 75.3o (2θ) corresponding to the study of heterogeneous catalyst materials.
crystal lattice planes (101), (103), (004), (112), Figure 6 presents the Raman spectrum in the
(200), (105), (211), (204), (116), (220), and (215), range of 100-800 cm−1 for the TiO2-QDs sample.
respectively. These peaks are characteristic of the Peaks at approximately 152, 195, 402, 520, and
crystalline phase structure of anatase, 645 cm−1 are assigned to the anatase phase of TiO2
corroborating previous XRD studies on TiO2 (space group D194h). These peaks correspond to
anatase phase samples [23,27,33]. Furthermore, five Raman-active modes with respective
Figure 4 demonstrates the absence of any symmetries: Eg(1), Eg(2), B1g, A1g + B1g (2), and
characteristic peaks for the rutile phase or any Eg(3) [38]. These results corroborate the
other crystalline phases. Calculate the average consistency between the XRD and Raman spectra.
particle size using XRD analysis results,
employing the Scherrer equation for the most 3.2 Photocatalytic Activity
intense (101) diffraction peak. The calculated
3.2.1 Investigate of the photocatalytic activity of
average size, D = 5.83 nm, closely aligns with the
TiO2 catalysts
value obtained via the TEM method. The anatase
phase of TiO2 is recognized for its superior The photocatalytic activity of TiO2 materials
photocatalytic capabilities, attributed to its higher was evaluated under the same optimal conditions,
electron mobility compared to the rutile phase. including the following parameters. Prior to
This property significantly enhances the efficiency irradiation, the catalyst was introduced into the
of pollutant degradation under UV light. methylene blue (MB) solution and continuously
The chemical composition of the TiO2-QDs stirred in darkness to assess the adsorption-
sample was analyzed using Energy Dispersive X- desorption equilibrium. Observations indicated
ray (EDX) spectroscopy (Figure 5), which that equilibrium was reached 30 min after the
indicated that the TiO2-QDs sample contains only addition of the catalyst, with no further changes
titanium and oxygen without any other noted upon extending the duration to 60 min. This
impurities. Raman spectroscopy provides suggests that the adsorption-desorption
valuable information about the purity and equilibrium was established within the first 30
crystallinity of a phase and is a powerful tool in min.
UV-Vis results confirmed that the
photocatalytic activity of the synthesized TiO 2
materials could be assessed using UV light due to
the wide bandgap of TiO2-QDs, which is 3.22 eV.
The photodegradation efficiency of methylene
blue by commercial TiO2, TiO2-NPs, and TiO2-QDs
catalysts is presented in Figure 7(a). The results
indicate that under the same experimental
conditions, the degradation of methylene blue
using the microwave-synthesized sample is
significantly higher than that of the two

Figure 4. XRD pattern of TiO2-QDs synthesized.

Figure 6. Raman Shift spectrum of TiO2-QDs

Figure 5. EDX spectrum of TiO2 quantum dot. sample.

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 Bulletin of Chemical Reaction Engineering & Catalysis, 19 (3), 2024, 413

Figure 7. Photodegradation efficiency of methylene blue by (a) different TiO2 catalyst, (b) TiO2-QDs dose,
(c) pH and (d) initial MB concentration.

Table 1. Comparison between this work and other already published. (ND: Not defined)
% of
No Precursor Sample Method Bandgap (eV) Treatment References
degradation
1 Ti(OBu)4 TiO2-QDsMicrowave- 3.22 MB 97.6 This study
assistant
2 - TiO2 CM Commercial ND MB 80 This study
3 - TiO2 NPs P25-Degussa 2.95 MB 93 This study
4 TTIP TiO2/HTC4 hydrothermal ND MB 91.9 [39]
5 ZAD ZnO Sol-gel 3.48 MB 99 [40]
6 ZAD ZnO Precipitation 3.31 MB 98 [40]
7 ZAD ZnO Thermal 3.27 MB 85 [40]
decomposition
8 Zn(NO3)2⋅6H2O ZnO/N-CQD hydrothermal 3.129 MB 80% Higher [41]
ZnO (after 30
mins)
9 TTIP TiO2 QDs Sol-gel 3.79 MB 97.9 [27]
10 TTIP TiO2 QDs Sol-gel 3.76 ND ND [25]
11 TiCl4 TiO2 QDs Sol-gel 2.85 MO Higher TiO2- [26]
P25
12 Ti(OBu)4 TiO2 QDs Sol-gel ND Indigo 100% [24]
Carmine
dye
13 TTIP TiO2 QDs hydrothermal 3.51 ND - [28]
14 TiBALDH and TiO2 QDs hydrothermal ND RhB and 100%, higher [29]
TiOCl2 MO TiO2-P25
15 Ti(SO4)2 TiO2 QDs hydrothermal 3.38, 3.47, ND ND [30]
3.25
16 Ti(OBu)4 TiO2 QDs Microwave- 3.69, 3.93, ND ND [31]
assistant 3.99, 4.35

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 Bulletin of Chemical Reaction Engineering & Catalysis, 19 (3), 2024, 414
commercial TiO2 samples, TiO2 NPs. Specifically, photons from reaching some of the catalyst
after 90 min of irradiation, the degradation particles, resulting in a reduction of the treatment
efficiency of MB for TiO2-QDs, TiO2 NPs, and TiO2 efficiency [43].
CM were 97.6%, 93%, and 80%, respectively. The results of the pH influence on the
Figure 7(a) shows that as the irradiation time solution, shown in Figure 7(c), demonstrate that
increases, the photocatalytic degradation with values ranging from 3 to 10, the efficiency
efficiency of MB also increases, indicating increases as the pH rises, reaching a maximum at
complete degradation of the dye. After 120 min of pH 7 and then gradually decreases up to pH 10.
irradiation, the degradation of the model reaction This trend is understandable given that the point
MB is almost complete for the microwave- of zero charge (pHpzc) is reported to be
synthesized TiO2-QDs sample, reaching 97.6%. It approximately 6.8 [44]. Therefore, changes in pH
is evident that TiO2-QDs have exhibited superior affect the adsorption capability of MB on TiO2-
photocatalytic degradation compared to nano- QDs material, consistent with findings from prior
sized TiO2 particle catalysts and commercial TiO2. research [43–45]. The investigation was
The difference in the degradation time of MB conducted with initial MB concentrations from 10
depends on the synthesis method, size, and to 50 mg/L. As depicted in Figure 7(d), the
morphology of the obtained materials. Indeed, the degradation efficiency of MB decreases with
improved photocatalytic activity of TiO2-QDs can increasing concentration. This is expected as a
be attributed to their quantum properties, such as higher MB concentration leads to increased MB
ultra-small particle size, and enhanced charge adsorption on the catalyst surface, thereby
carrier separation. These results are consistent hindering the reaction between MB and both the
with previous publications [25–27]. holes and hydroxyl radicals. Additionally, an
Table 1 presents several studies on the increase in MB concentration affects the proton
synthesis of materials and their ability to treat absorption efficiency of TiO2-QDs, resulting in a
organic compounds in water using photocatalytic reduced treatment efficacy as the MB quantity
materials. These studies demonstrate that self- increases [43].
synthesized quantum dot TiO2 is effective in
treating organic compounds and often 3.2.3 Research on the catalyst's reusability
outperforms TiO2 nanoparticles (P25-Degussa).
For industrial and environmental
Additionally, comparing the photocatalytic
applications, the catalyst's reusability is crucial to
activity and stability of different synthesized
determine its long-term stability and potential for
materials is challenging due to the many factors
reuse. To assess this important parameter, a long-
that influence the photocatalytic process [42].
term stability experiment was conducted over 5
Within the scope of this study, TiO2 quantum dots
consecutive photocatalytic cycles, as depicted in
exhibit superior methylene blue (MB) degradation
Figure 8. The catalyst materials were exposed to
efficiency compared to TiO2 nanoparticles and
light for 120 min. Following each cycle, the
TiO2 commercial material.
materials were separated using filtration and
centrifugation, and subsequently dried at 100 °C.
3.2.2 Investigating the factors affecting the
It can be observed that after all cycles, the
efficiency of catalysts
photocatalytic activity of the catalyst materials
The study of factors influencing the tested was lower than in the first cycle. Notably,
photocatalytic efficiency of TiO2-QDs for MB after 5 reuse cycles, the photodegradation
treatment involved sequentially altering efficiency of MB decreased from 97.6% to 94.5% for
variables including catalyst concentration, pH,
and initial concentration of MB to identify optimal
parameters. The investigation was conducted by
adjusting one parameter at a time while keeping
the others constant and irradiation time 120
minutes.
The investigation of TiO2-QDs concentration
ranging from 0.1 to 0.3 g/L, as shown in Figure
7(b), indicates that the degradation efficiency
gradually increases from a concentration of 0.1
g/L, reaches optimum concentration at 0.15 g/L,
and subsequently decreases as the concentration
reaches 0.3 g/L. This pattern suggests that
increasing concentration leads to a higher density
of active sites on the catalyst, thus enhancing the
degradation efficiency of MB. However, beyond a Figure 8. Reusability of commercial TiO2 catalyst
certain point, the excessive TiO2 particles obstruct and synthesized nano TiO2 catalysts.

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 Bulletin of Chemical Reaction Engineering & Catalysis, 19 (3), 2024, 415
the TiO2-QDs, from 93% to 78% for TiO2 NPs, and Declaration of Competing Interest
from 80% to 60% for the TiO2 CM. These results
We certify that this manuscript consists of
indicate that the synthesized TiO2-QDs catalyst
original, unpublished work which is not under
material exhibited better stability and reusability
consideration for publication elsewhere. We
compared to TiO2 NPs catalysts and commercial
declare no competing financial interest.
TiO2 CM. Indeed, the photocatalytic activity of
TiO2-QDs only showed a slight decrease, while the
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