Journal Pre-proof

Rind of Aloe vera (L.) Burm. f extract for the synthesis of titanium dioxide
nanoparticles: Properties and application in model dye pollutant degradation

Diana Vanda Wellia, Atika Fildza Syuadi, Resha Mutia Rahma, Atika Syafawi, M.
Rafli Habibillah, Syukri Arief, Kiki Adi Kurnia, Saepurahman, Yuly Kusumawati, Asep
Saefumillah
PII: S2666-0164(24)00021-5
DOI: https://doi.org/10.1016/j.cscee.2024.100627
Reference: CSCEE 100627

To appear in: Case Studies in Chemical and Environmental Engineering

Received Date: 5 November 2023

Revised Date: 10 January 2024
Accepted Date: 12 January 2024

Please cite this article as: D.V. Wellia, A.F. Syuadi, R.M. Rahma, A. Syafawi, M.R. Habibillah, S.
Arief, K.A. Kurnia, Saepurahman, Y. Kusumawati, A. Saefumillah, Rind of Aloe vera (L.) Burm. f
extract for the synthesis of titanium dioxide nanoparticles: Properties and application in model dye
pollutant degradation, Case Studies in Chemical and Environmental Engineering (2024), doi: https://
doi.org/10.1016/j.cscee.2024.100627.

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© 2024 Published by Elsevier Ltd.

 Rind of Aloe Vera (L.) Burm. f Extract for the Synthesis of Titanium
Dioxide Nanoparticles: Properties and Application in Model Dye
Pollutant Degradation

Diana Vanda Wellia*1, Atika Fildza Syuadi1, Resha Mutia Rahma1, Atika Syafawi1, M.
Rafli Habibillah1, Syukri Arief1, Kiki Adi Kurnia2, Saepurahman3, Yuly Kusumawati4,
and Asep Saefumillah5

1
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Andalas,
Padang, West Sumatera, 25163, Indonesia
2
Department of Chemical Engineering, Faculty of Industrial Technology, Institut Teknologi
Bandung, Jl. Ganesha No 10 Bandung 40132, Indonesia

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3
Research Center for Chemistry, National Research and Innovation Agency (BRIN), Gd. 452
KST BJ Habibie Serpong, Tangerang Selatan, Banten 15314, Indonesia

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4
Department of Chemistry, Faculty of Science and Analytical Data, Institut Teknologi Sepuluh
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Nopember, Kampus ITS Sukolilo, Surabaya 60111, Indonesia
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5
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas
Indonesia, Jl. Lingkar Kampus Raya, Depok, 16424, Indonesia
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Abstract: This study investigates the synthesis of TiO2 using the rind of Aloe vera (L.) Burm
extract as a green-capping agent. It was discovered that adding the studied extract up to 10%
(TOAv10) increased the surface area and pore volume while maintaining the spherical shape of
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the nanoparticles. Overall, the TOAv4 sample has the highest photocatalytic activity compared
to other samples and a good photocatalytic activity compared to TiO2 prepared without extract.
The current findings provide an environmentally friendly and low-cost protocol for the synthesis
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of TiO2 nanoparticles in the application of wastewater treatment.

Keywords: green synthesis, TiO2 nanoparticles, Aloe vera (L.) Burm. f, anatase

*Corresponding author: nandadiana@sci.unand.ac.id

1. INTRODUCTION

The development of nanoparticle materials has gotten much attention in recent years because
of their superior and unique properties compared to large-sized materials (1). Many studies have
attempted to develop nanoparticle materials such as Titanium oxide (TiO2). TiO2 is a metal oxide
semiconductor in both amorphous and crystalline forms, with the most common being rutile,
anatase, and brookite. Because of its high surface area, high potential energy for photo-
generated charge carriers, and superior photocatalytic activity, anatase is a preferred form. TiO2
has been used in various applications due to its remarkable properties, including wastewater
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treatment and the degradation of organic pollutants. Satinder K. Brar, et al. (2009) (2)have
emphasized the role of TiO2 nanoparticles in removing contaminants from water through
advanced oxidation processes, highlighting their potential in addressing water pollution
challenges. Additionally, the research presented by Chanani J, et al. (2023) (3) delves into the
application of nanoparticles in water treatment, emphasizing their ability to enhance the removal
of pollutants and improve overall water quality. The work reported by Tariq Khalafi, et al. (2019)
(4) explores the use of nanoparticles, including TiO2, for the degradation of organic pollutants,
demonstrating their effectiveness in promoting environmental sustainability. Furthermore, the
study by Mohapatra D, et al. (2014) (5) sheds light on the multifaceted role of nanoparticles in
addressing environmental challenges, emphasizing their potential in mitigating the impact of
organic pollutants on ecosystems. In summary, the literature suggests that nanoparticles,
particularly TiO2, play a crucial role in water treatment and the degradation of organic pollutants,

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offering promising solutions for environmental protection and sustainability.

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Numerous methods for producing TiO2 nanoparticles have been developed, including as sol–gel,

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hydrothermal, co-precipitation, direct oxidation method, electrodeposition, chemical vapor
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deposition, and green synthesis. Unlike the latter, most methods for producing TiO2
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nanoparticles were toxic and had negative environmental consequences. This is due to the use
of toxic solvents in the process, which can produce dangerous by-products (6), (7), (8). The
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precipitation method is one of the safe and effective methods for synthesizing nanoparticles,
which is based on the precipitation of a substance when it passes its saturation point. This
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method is easy and cheap because it can be used in low temperature with simple procedures
and requires a relatively short time. However, the precipitation method also tends to produce
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quite large particle sizes on the nanoscale. Therefore, in this study, an approach was carried out
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that could control the particle size to be smaller so that it could show better characteristics. One
way to do this is by adding a stabilizer through a green chemistry or green synthesis approach.

The green synthesis approach, rooted in green chemistry principles, holds considerable promise
for nanomaterial production by offering numerous advantages. Not only does it align with
environmentally friendly practices, but it also proves harmless, thereby addressing concerns
about toxicity during synthesis. Additionally, the green synthesis method contributes to reduced
synthesis times and costs, boasting easy and cost-effective reaction setups that align with the
principles of environmental sustainability and safety. Utilizing air as a solvent further diminishes
toxicity risks in the synthesis process. In essence, green synthesis emerges as a compelling
alternative, presenting a trifecta of benefits encompassing environmental safety, cost-
effectiveness, and synthesis simplicity (9). Recent trends in nanomaterial synthesis, particularly
for TiO2 nanoparticles, emphasize the adoption of green methods employing plant-based capping
agents. Phytochemical extracts sourced from various plant parts, such as leaves, roots, peels,
stems, flowers, and fruits, play a crucial role in this process. These extracts contain secondary
metabolites, including flavonoids, terpenoids, sugars, and polyphenols, believed to facilitate the
2
conversion of metal ions into TiO2 nanoparticles (10). The synthesis of TiO2 nanoparticles using
plant extracts is advantageous due to the presence of bioactive compounds that serve as natural
bioreductors and capping agents, effectively stabilizing the synthesized nanoparticles and
preventing agglomeration. It is noteworthy that beyond plant extracts, other biological materials
such as microorganisms and fungi also find application in the biosynthesis of nanomaterials (11–
13).

The synthesis of green chemistry-based nanoparticles can be carried out through a bottom-up
approach, namely combining small-scale materials (such as clusters) to form the desired
nanometer-scale particles. Plant-mediated synthesis of nanoparticles is a safe, environmentally
friendly, and more energy-efficient process (14). Phytochemicals in plants such as alkaloids,
amino acids, enzymes, phenolics, proteins, polysaccharides, saponins, terpenoids, and vitamins

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usually have the potential as stabilizers in the synthesis of nanoparticles. One such plant is Aloe

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vera (L.) Burm.f. The phytochemical screening of Aloe vera (L.) Burm.f. showed the alkaloid,
tannins, flavonoids, sterols, triterpenes, mucilages, oses, holosides and it reducing compounds

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metabolites (15). Those electron-rich phytochemical constituents present in Aloe vera (L.)
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Burm.f extract probably play a dual function as bioreductor and capping agents in the bioprocess
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of TiO2 NPs synthesis. In a preliminary activation phase, TiCl4 dissolves in deionized water, and
titanium ions would release from metallic salt precursor. The resultant then reacts with Aloe vera
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(L.) Burm.f derived electron-rich biomolecules including carbohydrates, vitamins, fiber, and fat
through a reduction-oxidation (donor-acceptor electron) mechanism. The significant reduction
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capabilities of those ample electron-donating biofunctional groups (R-OH, R-NH2, R-COO-) would
reduce titanium ions as electron acceptor from tetravalent oxidation state to zero-valent metal
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which instantly transform to TiO2 nanoparticles due to the high surface energy of nano-size
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titanium and presence of oxygen in reaction (16,17).

Several studies have been reported regarding the synthesis of TiO2 nanoparticles using plant
extracts. Rajkumari et al (2019), who researched the synthesis of TiO2 nanoparticles using an
Aloe barbadensis mill, explained that TiO2 nanoparticles are spherical with a size of 20 nm and
can reduce biofilm-related infections (14). Rao et al (2016) and Khadar et al. (2016) reported a
similar matter in the manufacture of TiO2 nanoparticles using Aloe vera extract with the result
that the particle structure was irregular and the average particle size reached 32 nm in the
synthesis results (18), (19). Based on these researches, it can be seen that plants and Aloe vera
extracts have been successfully carried out in the formation of TiO2 nanoparticles. In prior
research, Aloe vera (L.) Burm. f extract was utilized in the synthesis of N-doped TiO2, which
commenced with a biosynthesis process of TiO2 followed by the introduction of nitrogen via the
hydrothermal method. From this study, N-doped TiO2 with homogeneous spherical morphology
and particle sizes ranging from 15-55 nm were obtained (20). However, the characteristics of
the biosynthesized TiO2 material itself (without doping) utilizing Aloe vera (L.) Burm. f extract
have not been further investigated. Therefore, this research will study the differences in the
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characteristics of TiO2 nanoparticles synthesized using Aloe vera (L.) Burm extract. f. and to see
the optimum amount of extract addition in producing TiO2 nanoparticles. Here, the as-prepared
TiO2 nanoparticles will be characterized via Fourier-Transform Infrared (FTIR) spectrometer, X-
ray diffraction (XRD), Diffuse Reflectance Spectroscopy (DRS) UV-Vis, Thermogravimetry-
Differential Thermal Analysis (TG-DTA), Scanning Electron Microscopy-Energy Dispersive X-ray
spectroscopy (SEM-EDX), Transmission Electron Microscopy (TEM), and Brunauer-Emmett-Teller
(BET). The effect of the capping agent on size, morphology, optical, structural properties, and
photoactivity for the degradation of methylene blue was also investigated.

2. EXPERIMENTAL SECTION

2.1. Materials

Titanium tetrachloride (TiCl4, 1M in Methylene Chloride, Merck), Sodium hydroxide (NaOH,

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Merck), and ethanol (C2H5OH, p.a Merck) were used as received. Deionized water was used
throughout the experiment. Deionized water was utilized consistently throughout the

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experiment. Plant samples of Aloe vera (L.) Burm. f. were obtained from both the skin and gel.
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The botanical identification of the plant was conducted at the Herbarium Laboratory of
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Universitas Andalas (ANDA), Department of Biology, Faculty of Mathematics and Natural
Sciences, Universitas Andalas, Padang, Indonesia.
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2.2. Preparation of Aloe vera (L.) Burm. f. rind extract

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The fresh rind of Aloe vera (L.) Burm. f. was carefully separated from the gel, cleaned, and
mashed. The extract was prepared by dissolving 10 g of the mashed rind in 100 mL of deionized
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water and stirring for 1 hour at 70˚C. To obtain a clear solution, the rind extract was filtered
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through a Whatman filter paper (No. 42).

2.3. Synthesis of TiO2 nanoparticles

About 5 mL of titanium chloride (TiCl4, 1M) solution was added into a 100 ml round bottom flask,
followed by 50 mL of deionized water, slowly added while stirring. Then, 4% (volume/volume)
of Aloe vera (L.) Burm. f. rind extracts were added dropwise, followed by 1 M NaOH aqueous
solution to pH=7 and stirred for 24 hours to synthesize TiO2, later referred to as TOAv4. The
residue was obtained by centrifugation (1600 rpm, 25˚C) and then washed three times with
ethanol and distilled water to remove impurities before drying (oven, LabTech) at 100 C for 10
hours. The powder was calcined at 500˚C for 1 hour, and the final product was labelled TOAv4.
The same procedures were followed for the addition extract of 10% v/v (TOAv10) and 20% v/v
(TOAv20). Un-capped TiO2 was prepared as a control for comparison using a similar procedure,
but with no extract and only de-ionized water, and labelled with TO. The details of the samples
are shown in table 1.

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Table 1 Variation of precursor and Aloe vera (L.) Burm. f. rind extracts volume ratio
No. Sampel Code Percent Volume (mL) ratio
extact (v/v) precursor/extract
1 TO 0 5: 0
2 TOAv4 4% 5: 0.2
3 TOAv10 10% 5: 0.5
4 TOAv20 20% 5:1

2.4. Characterization

FTIR Spectrometer (PerkinElmer FT-IR Spectrometer Frontier) was used for functional group
analysis at 500–4000 cm-1. The crystalline profile of TiO2 nanoparticles was investigated in the
absence and presence of various concentrations of plant extract via X-ray diffraction (XRD) using

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XPERT PRO PAnalytical PW 30/40 X-ray diffractometer in the range of 10–80° and resolution of
2° with Cu Kα radiation (wavelength, λ = 1.5406 Å). UV − vis diffuse reflectance spectra were

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obtained using a spectrophotometer (SPECORD 210 Plus). Scanning Electron Microscopy (SEM)
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(Hitachi FLEXSEM 1000) and Transmission Electron Microscopy (TEM) (200 Kv Tecnai G20 S-
Twin) were used to examine the surface morphology and particle size of the catalyst.
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Thermogravimetric analysis (TGA) was conducted using DTG-60 SIMULTANEOUS DTA-TG
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APPARATUS SHIMADZU at a heating rate of 10 °C/min from 0 to 800 °C.

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2.5. Photocatalytic activity test on methylene blue (MB) removal

Using an ultrasonic bath, 50 mg of the photocatalyst was dispersed in 10 mL of Mili Q water for
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10 minutes (Granbo). In a crystallization dish, the photocatalyst dispersion was mixed with 40
mL of MB 40 ppm stock solution. The crystallization dish was placed inside the UV-C chamber
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(59.549.550 cm3). This chamber was equipped with a 15 W Philips TUV 15W/G15 T8, emitting
UV-C light at a wavelength of 254 nm. The light source was oriented perpendicular to the sample
at an angle of 180º, and the distance between the sample and the lamp was maintained at 14
cm. This experimental configuration resulted in an average photon flux, on an amount basis,
denoted as (qn,p), measuring 2.8716 × 10–5 einstein s⁻¹. The inner wall of the box was layered
with reflective material to maximize UV-C irradiation. After 60 minutes of irradiation, 1000 L of
the suspension was centrifuged for at least 10 minutes at 7000 rpm (Dlab). Using an Agilent
Cary-60 UV-Vis spectrophotometer, the clear solution's absorbance wavelength of 665 nm was
measured. The percentage of removal is calculated as the difference in absorbance of the solu-
tion after t min (At) and absorbance at 0 min (A0) as shown in equation 1.

𝑨𝟎 − 𝑨𝒕
%removal = x 100 (1)
𝑨𝟎

For comparison, dark experiments were performed using the same protocol but without the lamp
turned on. Each experiment was carried out twice, with the average data reported.

5
3. RESULTS AND DISCUSSION

3.1 The Analysis of FTIR Spectra of Extract and TiO2 Nanoparticles

Figure 1. presents the FTIR spectra of the extract and the synthesized TiO2 nanoparticles at
different functional groups present in each system. Figure 1.a shows the FTIR spectrum of an
Aloe vera (L.) Burm. f. rind extract. The wide bands at 3333 cm-1 indicated the stretching of the
phenolic hydroxyl groups' O-H bonds (5). The peak of 2100 cm-1 indicates the C=C stretching
vibration of the aromatic ring (21). The C=O bond stretching of the carbonyl group or the C=C
bond stretching at ɑ-ꞵ-unsaturated ketone is shown by the absorption band of 1630 cm-1 (22). It
is likely that the organic compounds such as phenolic, anthraquinone, flavonoid, and terpenoid
present in Aloe vera (L.) Burm. f. rind extract stabilizes TiO2 nanoparticles (14,21).

Figure 1b-c presents the FTIR spectra of the synthesized TiO2. The broadband appeared at

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around 3000 to 3600 cm−1 in all spectra, indicating the stretching vibration of –OH groups, while
the peaks centered at 1630 cm−1 indicate the bending vibration of –OH groups. It is observed

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that the capped TiO2(s) spectra are similar to that of uncapped TiO2. Likely, the bonding of the
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capping agent to the TiO2 did not influence the structural patterns present in the uncapped TiO2.
The appearance of a sharp band at 540 cm-1 indicates the Ti-O-Ti lattice stretching vibration of
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anatase TiO2 (23).
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540

b
% Transmittance

1630
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1219 1150
3100-3700
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a
2100

1630
3333

4000 3500 3000 2500 2000 1500 1000 500

-1
Wavenumber (cm )
Figure 1: FTIR spectrum of (a) Aloe vera (L.) Burm. f. rind extract and TOAv10 nanoparticles:
(b) before and (c) after calcination

3.2 TiO2 Nanoparticles Product

The synthesis of TiO2 nanoparticles was carried out in the absence and presence of 4%, 10%,
and 20% of Aloe vera (L.) Burm. f. rind extract with labels TO, TOAv4, TOAv10, and, TOAv20,
respectively. All the synthesized TiO2 are a fine white powder, as shown in Figure 2.

6
 (a) (b) (c) (d)

Figure 2: Photo of samples of synthesized TiO2 nanoparticles: (a) TO, (b) TOAv4, (c) TOAv10,
and (d) TOAv20

The TiO2 nanoparticles are formed via the reaction mechanism shown in Scheme 1. The
bioreduction mechanism described herein bears a resemblance to the antioxidant mechanism,

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particularly in the interaction between 2,2-diphenyl-1-picrylhydrazyl (DPPH) and the antioxidant

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compound ArOH. Homolytic cleavage of the antioxidant compound induces the formation of ArO•
and H•. Subsequently, hydrogen radicals affiliate with the hydroxyl groups on the [Ti(OH)4]

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complex, generating H2O• groups. The H2O• moiety instigates homolytic bond rupture in the Ti-
O coordination covalent bond, causing the reduction of Ti4+ to Ti3+ by gaining one electron. This
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yields [•Ti(OH)3] and releases H2O. Due to its inherent instability, Ti3+ readily relinquishes an
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electron, which is subsequently assimilated by the hydroxyl group, yielding •O-H. The hydroxyl
radical triggers the homolytic cleavage of •O-H, leading to the formation of O2- and H•. Under
these conditions, Ti4+ and O2- are already ionically bonded, while the presence of H• catalyzes
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analogous reactions on other hydroxyl groups. Ultimately, this sequence culminates in the
production of TiO2, accompanied by the recovery of secondary metabolite compounds. The
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reducing ability increases due to the oxidation of the plant extract and the formation of new
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components, which contributes to an increase in stability(13).

3.3 Analysis of Crystal Structure and Sample Purity

Figure 3. shows the structures of TiO2 nanoparticles in the absence and presence of various
concentrations of plant extract. The major peaks are visible in the XRD patterns of the uncapped
TiO2, which was prepared without adding plant extract with the Bragg reflection of 2𝜃 at 25.48˚,
37.96˚, 48.00˚, 54.41˚, 62.68˚, and 75.31˚ correspond to the plane (101), (004), (200), (105),
(204), and (215), respectively (9). This result validates that TiO2 nanoparticle formation has a
pure anatase phase (ICSD standard 9855). Comparable XRD patterns were also observed for
the capped TiO2 nanoparticles. Thus, the XRD measurements reveal that adding plant extract
did not alter the crystal structure of TiO2 nanoparticles. It is also found an impurity peak in the
form of NaCl in all samples, as shown in Figure 3. The interaction of Cl causes the impurity peak
ions in the precursor with Na+ in NaOH, resulting in the formation of a salt (NaCl) as a by-product
that is trapped by the extract during the TiO2 nanoparticle formation process (11), (12), (24).

7
XRD analysis is used to assess the crystallite size of the samples using Scherrer's formula. The
crystallite size of TO, TOAv4, TOAv10 and ToAv20 was 9.65 nm, 13.57 nm, 10.46 nm, and 9.32
nm, respectively. These findings support using plant extracts with smaller crystallite sizes in the
sample.

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Scheme 1: The reaction mechanism for the formation of TiO2 nanoparticles mediated by Aloe
vera (L.) Burm. f. rind extract

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 a (101)
* NaCl

a (105)
a (004)

a (200)

a (215)
a (204)
*
*
d

c
Intensity (a.u.)

Anatase

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20 30 40 50 60 70 80
2θ (°)

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Figure 3: XRD diffraction pattern of TiO2 nanoparticles: (a) TO, (b) TOAv4, (c)
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TOAv10, and (d) TOAv20
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3.4 Analysis of Optical Properties
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The number of incident photons absorbed during the photocatalytic process is described by
optical properties, which are essential for photocatalytic research. Figure 4. depicts the UV-Vis
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DRS spectrum absorbing at UV light wavelengths for all samples of TiO2 nanoparticles. According
to the UV-Vis absorption spectra, the higher absorption is in the 326-330 nm range, indicating
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the formation of TiO2 nanoparticles. This result is comparable to TiO2 nanoparticles synthesized
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using the Aloe barbadensis mill, as reported by Rajkumari et al. (25). The UV spectrum result
shows that adding the extract did not significantly change the spectral peaks for each sample.
Band gap energies were found for TO (3.13 eV), TOAv4 (3.15 eV), TOAv10 (3.16 eV), and
TOAv20 (3.18 eV).

Figure 4: DRS UV-Vis spectra of TiO2 samples: TO, TOAv4, TOAv10, and TOAv20

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3.5 Surface Morphology Analysis
The shape, morphology, and apparent grain size of the synthesized TiO2 nanoparticles were
examined using Scanning Electron Microscopy (SEM). As shown in Figure 5a-c, the TiO2
particles are uniformly distributed and spherical, ranging in size from 14 to 24 nm (measured
by ImageJ). The reduced nanoparticle size indicates the extract's effect on the formation of TiO2
nanoparticles. The effect becomes more pronounced when the plant extract concentration is
increased to 10%. However, adding the plant extract up to 20%, as in the case of TOAv20,
altered the shape of TiO2 nanoparticles to become irregular and rod-shaped. Because of the
increased interaction between extracts and precursors, particles cluster and agglomerate,
forming aggregates into larger particles (4). As a stabilizer, the extract becomes less effective,
and particle size increases and is not uniform (26), (27).

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Figure 5: SEM photos of TiO2 nanoparticles: (a) TO, (b) TOAv4, (c) TOAv10, and (d) TOAv20

3.6 Transmission Electron Microscope (TEM) Analysis

The shape and size of nanoparticles were further analyzed by advanced technique transmission
electron microscopy (TEM). Figure 6. shows the TEM image of the TOAv4 and TOAv10 samples.
As can be observed, the synthesized TiO2 nanoparticles with 4% extract are spherical, which is
10
in complete agreement with SEM results. Conversely, Figure 6(c) shows the TEM image of
sample TOAv10 with a smaller particle size and more agglomeration than sample TOAv4.

(a) (b)

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(c) (d)
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Figure 6: TEM images of: (a, b) TOAv4 sample and (c, d) TOAv10 sample
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Energy-dispersive X-ray (EDX) spectroscopy assessed the elemental composition of TiO2

nanoparticle samples. Figure 7. shows the EDS patterns of the synthesized TiO2 nanoparticles.
The EDS patterns of the synthesized TO, TOAv4, TOAv10, and TOAv20 nanoparticle samples
show sharp and strong characteristic peaks in titanium (Ti) and oxygen (O), confirming the
formation of TiO2 nanoparticles from plant extracts. The Inset of Fig. 7 is the weight and atomic
percentages of TiO2 nanoparticles. The EDX measurements validate the presence of titanium and
oxygen atoms with small impurities, such as Na, Cl, and Si atoms. Na and Cl are present due to
the interaction of substances between Cl- ions from the precursor and NaOH to form a salt (NaCl)
as a by-product (11), (12), (24). Si is present due to the glass substrate used for the film
preparation or the detector in the EDX (28).

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Figure 7: EDX spectrum of TiO2 nanoparticles: (a) TO, (b) TOAv4, (c) TOAv10, and (d)

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TOAv20

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3.7 Surface Area Analysis -p
The surface area for the synthesized TiO2 nanoparticles is measured via Brunauer–Emmett–
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Teller (BET). Fig. 8 shows the characteristic plot of N2 adsorption–desorption isotherm and pore
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size distribution curves of the as-prepared TiO2 nanoparticles. All TiO2 nanoparticles synthesized
exhibited the isotherm of type-IV (BDDT classification) as a mesoporous solid with a pore size
of 6-8 nm (29).
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Table 2 summarises the results from the BET analysis, including specific surface area, pore
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diameter, and pore volume for the synthesized TiO2 nanoparticles in the absence and presence
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of plant extract. The uncapped TiO2 nanoparticles had a BET surface area of approximately 66.11
m2/g. Adding up to 10% plant extract increases the BET surface area of the synthesized TiO2
nanoparticles. Higher surface area can provide more surface-active sites for reactive molecule
adsorption, making the photocatalytic process more efficient. However, further addition of up to
20% of plant extract led to decreased BET surface area that could be attributed to the
accumulation of the TiO2 nanoparticles. A higher concentration of plant extract has probably
shielded the active nucleation sites, whereas a lower concentration caused insufficient capping.

Table 2: Results of BET for specific surface area, pore diameter, and pore volume

Number Sample Specific surface area (m2/g) Pore diameter (nm) Pore volume (mL/g)

1 TO 66,11 6,442 0,213

2 TOAv4 67,60 6,704 0,234
3 TOAv10 68,46 6,776 0,235
4 TOAv20 51 8,058 0,211

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 150
150

125
125

100

Volume (mL/g)

Volume (mL/g)
100

75
75

50
50

25 25

0 0
0,0 0,2 0,4 0,6 0,8 1,0 0,0 0,2 0,4 0,6 0,8 1,0
P/P0 P/P0
(a) (b)

150
150

125
125

100
Volume (mL/g)

Volume (mL/g)
100

f
75

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75

50 50

r
25 25

0
0,0 0,2 0,4
P/P0
0,6 0,8
-p1,0
0
0,0 0,2 0,4
P/P0
0,6 0,8 1,0
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(c) (d)

0,5
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0,4
TO
dV[log(r)] (cm3/g)

TOAv4
TOAv10
0,3
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TOAv20

0,2

0,1
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0,0
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0 20 40 60 80 100 120 140 160 180 200

Pore radius (nm)
(e)

Figure 8: BET isotherm curve of (a) TO, (b) TOAv4, (c) TOAv10, (d) TOAv20, and (e) the pore
size distributions curve of TO, TOAv4, TOAv10, TOAv20

3.8 Thermal Property Analysis

The TGA thermogram reveals the weight loss during an increased temperature, while the DTA
thermogram highlights the heat involved in each mass change process. Fig. 9 shows the TG-DTA
thermogram of the TOAv10 sample before (Fig. 9.a) and after calcination (Fig. 9.b). Fig. 9a
depicts the 18% weight loss in the TG thermogram caused by the evaporation of organic matter
associated with the extract, which is responsible for preventing aggregation and maintaining a
uniform TiO2 nanoparticle size (29). Furthermore, weight loss was observed at temperature close
to 110°C due to moisture loss in the sample, which could have resulted from water molecules
adsorbed on the surface (30). In the DTA thermogram, both processes have an endothermic
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peak at 80°C. (blue curve). The weight loss at 280°C with an exothermic peak is associated with
pyrolysis and carbonization processes (21). The evaporation of carbonization residue on the
surface of the synthesized nano sample was then associated with weight loss and an exothermic
peak around 400°C (21). Weight loss at a temperature higher than 400ºC indicated the
formation of TiO2 nanoparticles from amorphous to anatase (31).

Fig. 9b shows the TG-DTA thermogram of the TOAv10 sample after calcination. Fig. 8b shows a
weight loss of 7% in the TG thermogram at 60ºC and 110ºC. The weight loss indicates that there
is still moisture in the sample, likely from the water molecules adsorbed on the surface (30).
This process is characterized by an endothermic peak in the DTA thermogram at 60oC. (blue
curve). The weight loss at 250°C is due to incomplete evaporation of organic matter before
calcination, causing the pyrolysis and carbonization processes to repeat, as indicated by an

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exothermic peak in the DTA thermogram at that temperature (21). The evaporation of the

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carbonization residue was also associated with weight loss and an exothermic peak around 450°C
(21). No significant weight loss was observed after 450°C, indicating the formation of anatase-

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phase TiO2 nanoparticles (31). At 730ºC, there was a slight weight loss and an increase in the
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exothermic peak due to a phase change from anatase to rutile.
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100
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95
95
TG
90
Weight Loss (%)

90
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Weight Loss (%)

85

exo DTA
85
exo DTA
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80
80

75 DTA
75
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70 70

65 65
0 100 200 300 400 500 600 700 800 0 100 200 300 400 500 600 700 800
Temperature (°C) Temperature (°C)
(a) (b)

Fig. 9. TG-DTA thermogram of TOAv10 sample: (a) before and (b) after calcination

3.9 Removal of Methylene Blue (MB) Dye Studies

Fig. 10 depicts the results of photocatalytic degradation studies of the synthesized TiO2 catalyst
for the degradation of the MB solution. The test was carried out in two conditions: without and
with irradiation. The bandgap model of semiconductors, which is composed of band frameworks,
valance band (VB), and conductance band (CB) that detached with an energy gap, can be used
to interpret aqueous photocatalytic degradation of organic materials (Eg) (32). TiO2 has a large
band gap energy that can be excited by high-energy light. Nanoscale particle sizes can also
increase band gap energy, resulting in excitation energy elaboration due to the quantum

15
confinement effect. The greater the band gap energy, the more energy is required to excite
electrons to the conduction band.

without irradiation 88,84

with irradiation

80

60

% degradation
51,44
48 49,29
47,82

40

20

7,38
4,87
1,97 3,04
0
0

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TO TOAv4 TOAv10 TOAv20 TiO2 P25

Samples

Fig. 10. Percentage of degradation ability for methylene blue of synthesized TiO2 sampes

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with/without visible light irradiation
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The degradation percentages of TO, TOAv4, TOAv10, and TOAv20 samples were 48%, 51.44%,
47.82%, and 49.29%, respectively, as shown in Fig. 10. The irradiation greatly affects the
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photocatalytic activity of the sample in degrading methylene blue. Irradiating TiO2

semiconductors causes electron-hole charge carriers to form, promoting the photodegradation
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of MB solutions. The adsorbed O2 can capture the generated electrons to form O2-, and the holes
can be trapped by the OH- surface to form OH. This O2- and OH are crucial in the
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photodegradation of MB solutions.
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However, despite having better characteristics than the other samples, the TOAv10 sample had
lower photocatalytic activity than the TOAv4 sample. In the TOAv10 sample, more agglomerates
cause this, reducing its ability to degrade MB. The following formulas describe the mechanism
reaction of photodegradation of MB solution:

Finally, the photocatalytic efficiency observed in the degradation of methylene blue,

utilized as a model pollutant in this study, is compared with existing literature. A
comprehensive review of the literature reveals a limited demonstration of methylene
16
blue degradation through TiO2 nanoparticles synthesized by various methods, as
summarized in Table 3. The comparative analysis presented in the table indicates that
the current investigation exhibits a relatively superior photocatalytic performance in the
degradation of methylene blue dye compared to the findings reported in the literature.
This outcome underscores the potential efficacy of utilizing Aloe vera rind extract in the
synthesis of TiO2 nanoparticles, showcasing a promising avenue for achieving high
performance in photocatalysis.

Table 3: Comparison of photocatalytic activity of biosynthesized-TiO2 nanoparticle

towards Methylene blue degradation

No Plant category MB dye removal (%) Condition Reference

and time required

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1. Commelina benghanlensis 65%, 120 min Under UV Hintsho-Mbita NC,
light et al (2023)

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2. Leaf Extract of Citrus Au- 94%, 180 min Under UV K. R. Murali, et al

3.
rantifolia

Jasmine flower extract

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92%, 120 min
light

Under UV
(2021)

Mary MSM, et al
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light (2021)

4. Leaf extract of Parthenium 92.5%, 6 h Under UV Tiwari M, et al

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hysterophorus light (2018)

5. Acalypha indica 82.6%, 6 h Under UV Nasif O, et al

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light (2023)
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4. CONCLUSION

This study has successfully synthesized TiO2 nanoparticles using the mediation of Aloe vera (L.)
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Burm. f. rind extract. All TiO2 nanoparticles exhibit an anatase phase with NaCl as an impurity.
The sample can absorb UV light with a peak absorption wavelength of 326-330 nm. Thermal
analysis revealed the formation of anatase TiO2 nanoparticles in the 400ºC-500ºC temperature
range. EDS analysis reveals elements like Ti and O. FTIR analysis reveals the presence of
stabilizing agents. The morphology of TO, TOAv4, and TOAv10 is spherical, whereas TOAv20 is
rod-shaped due to aggregation, as revealed by SEM. The particle sizes of TO, TOAv4, TOAv10,
and TOAv20 samples were 23.4 nm; 16 nm; 14 nm, and 18 nm, respectively. The BET surface
area analysis revealed that the TOAv10 sample had the highest specific surface area and pore
volume compared to other samples, namely 68.46 m2/g and 0.235 mL/g, indicating that the
TOAv10 sample interacted more easily and was more reactive. Compared to TiO2 prepared
without extract, the photocatalytic activity of TOAv4 (4%wt extract addition) demonstrates the
best activity on methylene blue removal. The excellent photocatalytic activity of synthesized TiO2
nanoparticles demonstrates that the prepared photocatalyst is safe for the environment and has
potential applications for removing dye from aqueous solutions.

17
5. CONFLICT OF INTEREST

The authors declare no competing financial or conflict of interest.

6. ACKNOWLEDGMENTS

This work was developed under the "Riset Kolaborasi Indonesia" program 2022 (reference
number: 2328/IT1.BO7.1/KU.02/2022). DVW would like to acknowledge Universitas Andalas for
the research contract with reference number T/36/UN.16.17/PT.01.03/IS-RKI. DVW is grateful
to Emil Salim, M.Si, M.Sc, for guiding the mechanism of TiO2 biosynthesis using the rind of Aloe
vera (L.) Burm extract.

7. REFERENCES

f
oo
1. Mandai PK, Choi K, Min SG, Lee CH. Application of nanotechnology in food packaging: an
overview. Korean J Food Sci Anim Resour. 2009;29(4):403–8.

2. Brar SK, Verma M, Tyagi RD, Surampalli RY. Engineered nanoparticles in wastewater and

r
-p
wastewater sludge - Evidence and impacts. Vol. 30, Waste Management. 2010. p. 504–
20.
re
3. Chanani J, BF& NY. Promoted Photocatalytic Activity of Green Titanium Oxide-Clay
Nanocomposite Toward Polychlorinated Biphenyl Degradation in Actual Samples. Water
lP

Air Soil Pollut. 2023;234–364.

4. Khalafi T, Buazar F, Ghanemi K. Phycosynthesis and Enhanced Photocatalytic Activity of

Zinc Oxide Nanoparticles Toward Organosulfur Pollutants. Sci Rep. 2019 Dec 1;9(1).
na

5. Mohapatra DP, Brar SK, Daghrir R, Tyagi RD, Picard P, Surampalli RY, et al. Photocatalytic
degradation of carbamazepine in wastewater by using a new class of whey-stabilized
ur

nanocrystalline TiO2 and ZnO. Science of the Total Environment. 2014 Jul 1;485–
486(1):263–9.
Jo

6. Sundrarajan M, Gowri S. Green synthesis of titanium dioxide nanoparticles by Nyctanthes

arbor-tristis leaves extract. Chalcogenide Letters. 2011;8(8):447–51.

7. Goutam SP, Saxena G, Singh V, Yadav AK, Bharagava RN, Thapa KB. Green synthesis of
TiO2 nanoparticles using leaf extract of Jatropha curcas L. for photocatalytic degradation
of tannery wastewater. Chemical Engineering Journal. 2018;336:386–96.

8. Mohammadlou M, Jafarizadeh-Malmiri H, Maghsoudi H. Hydrothermal green synthesis of

silver nanoparticles using Pelargonium/Geranium leaf extract and evaluation of their
antifungal activity. Green Processing and Synthesis. 2017;6(1):31–42.

9. Bourikas K, Kordulis C, Lycourghiotis A. Titanium dioxide (Anatase and Rutile): Surface

chemistry, liquid-solid interface chemistry, and scientific synthesis of supported catalysts.
Vol. 114, Chemical Reviews. American Chemical Society; 2014. p. 9754–823.

10. Abisharani J, Kumar Rd. Green synthesis of TiO2 Nanoparticles using Cucurbita pepo seeds
extract. Vol. 14, Materials Today: Proceedings. 2019. Available from:
www.sciencedirect.comwww.materialstoday.com/proceedings2214-7853

11. Rasheed RT. Al-Mustansiriyah Journal of Science Preparation and Characterization of TiO2
Nanostructure by TiCl4 Hydrolysis with Additive NaOH.

12. Nurbayasari R, Saridewi N, Pusat S, Dan P, Daya P, Produk S, et al. Biosintesis dan
Karakterisasi Nanopartikel ZnO dengan Ekstrak Rumput Laut Hijau Caulerpa sp.
18
 Biosynthesis and Characterization of ZnO Nanoparticles with Extract of Green Seaweed
Caulerpa sp. Jurnal Perikanan Universitas Gadjah Mada. 19(1):17–28.

13. Vasyliev G, Vorobyova V, Skiba M, Khrokalo L. Green Synthesis of Silver Nanoparticles

Using Waste Products (Apricot and Black Currant Pomace) Aqueous Extracts and Their
Characterization. Advances in Materials Science and Engineering. 2020;2020.

14. Rajkumari J, Magdalane CM, Siddhardha B, Madhavan J, Ramalingam G, Al-Dhabi NA, et

al. Synthesis of titanium oxide nanoparticles using Aloe barbadensis mill and evaluation
of its antibiofilm potential against Pseudomonas aeruginosa PAO1. J Photochem Photobiol
B. 2019;201(May):111667.

15. Benzidia B, Barbouchi M, Hammouch H, Belahbib N, Zouarhi M, Erramli H, et al. Chemical

composition and antioxidant activity of tannins extract from green rind of Aloe vera (L.)
Burm. F. J King Saud Univ Sci. 2019 Oct 1;31(4):1175–81.

16. Koopi H, Buazar F. A novel one-pot biosynthesis of pure alpha aluminum oxide
nanoparticles using the macroalgae Sargassum ilicifolium: A green marine approach.
Ceram Int. 2018 Jun 1;44(8):8940–5.

f
oo
17. Buazar F, Baghlani-Nejazd MH, Badri M, Kashisaz M, Khaledi-Nasab A, Kroushawi F. Facile
one-pot phytosynthesis of magnetic nanoparticles using potato extract and their catalytic
activity. Starch/Staerke. 2016 Jul 1;68(7–8):796–804.

r
18. -p
Technology C. Green Synthesis of TiO2 Nanoparticles Using Aloe Vera Extract.
2016;2(January 2015):28–34.
re
19. Abdul Khadar, Dilip Kumar B, Kalyan Kumar M. Synthesis and Characterization of
controlled size TiO2 nano particles via Green Route using Aloe vera extract. International
lP

journal of science and research. 2016;5(11):1913–6.

20. Wellia DV, Habibillah MR, Syafawi A, Rahmadini R, Rahmayeni R, Pratiwi N. A New
Combination Method of N-doped TiO2 Nanoparticles Synthesis for Heavy Metal Ions Cr(VI)
na

Photoreduction Applications. Jurnal Kimia Sains dan Aplikasi. 2023 Mar 31;26(2):70–8.

21. Bekele ET, Gonfa BA, Zelekew OA, Belay HH, Sabir FK. Synthesis of Titanium Oxide
ur

Nanoparticles Using Root Extract of Kniphofia foliosa as a Template , Characterization ,

and Its Application on Drug Resistance Bacteria. 2020;2020:1–10.
Jo

22. Ambika S, Sundrarajan M. [EMIM] BF4 ionic liquid-mediated synthesis of TiO2

nanoparticles using Vitex negundo Linn extract and its antibacterial activity. J Mol Liq.
2016;221:986–92.

23. Abisharani JM, Devikala S, Dinesh Kumar R, Arthanareeswari M, Kamaraj P. Green

synthesis of TiO2 nanoparticles using Cucurbita pepo seeds extract. Mater Today Proc.
2019;14:302–7.

24. Jadhav DB. Characterization of TiO2 Metal Oxides Nanoparticle Synthesized using Plant
extracts and Fabrication of “Solar Cell” using ITO glass, TiO2 , Ruthenium, Graphite and
Potassium Iodide. 2019. Available from: https://hq.ssrn.com/conference=2019-APGRES

25. Fajaroh F. Sintesis Nanopartikel dengan Prinsip Kimia Hijau. Seminar Nasional Kimia dan
Pembelajarannya (SNKP) 2018. 2018;03(November):24–32.

26. Ningsih N, Yasni S, Yuliani S. Sıntesıs Nanopartıkel Ekstrak Kulıt Manggıs Merah Dan Kajıan
Sıfat Fungsıonal Produk Enkapsulasınya. Jurnal Teknologi dan Industri Pangan [Internet].
2017 Jun 30;28(1):27–35. Available from:
http://journal.ipb.ac.id/index.php/jtip/article/view/15599

27. Dwipa R, Away Y, Fujii S, Ban T, Ohya Y. Preparation of Mesoporous Titania Thin Films
and Their Photocatalytic Activity.

19
28. Krishnasamy A, Sundaresan M, Velan P. Rapid phytosynthesis of nano-sized titanium using
leaf extract of Azadirachta indica. Vol. 8, International Journal of ChemTech Research
CODEN. 2015.

29. Al-Shabib NA, Husain FM, Qais FA, Ahmad N, Khan A, Alyousef AA, et al. Phyto-Mediated
Synthesis of Porous Titanium Dioxide Nanoparticles From Withania somnifera Root
Extract: Broad-Spectrum Attenuation of Biofilm and Cytotoxic Properties Against HepG2
Cell Lines. Front Microbiol. 2020 Jul 28;11.

30. Kashale AA, Gattu KP, Ghule K, Ingole VH, Dhanayat S, Sharma R, et al. Biomediated
green synthesis of TiO2 nanoparticles for lithium ion battery application. Compos B Eng.
2016 Aug 15;99:297–304.

31. Wellia D V., Xu QC, Sk MA, Lim KH, Lim TM, Tan TTY. Experimental and theoretical studies
of Fe-doped TiO2 films prepared by peroxo sol-gel method. Appl Catal A Gen. 2011 Jul
15;401(1–2):98–105.

32. Mishra S, Chakinala N, Chakinala AG, Surolia PK. Photocatalytic degradation of methylene
blue using monometallic and bimetallic Bi-Fe doped TiO2. Catal Commun. 2022 Nov 1;171.

f
r oo
-p
re
lP
na
ur
Jo

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Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐ The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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